1,2,6-Triphenyl-4(1H)-pyridinone derivatives, and their use as fungicides

ABSTRACT

New substituted derivatives of 1,2,6-triphenyl-4(1H)-pyridone are now provided, which are useful as fungicidal agent having practically valuable and improved fungicidal activities against a variety of phyto-pathogenic microorganisms, especially fungi and which show low toxicity to animals, including humans. These new compounds may be produced by different processes.

This application is a continuation of Ser. No. 029,944, filed Mar. 26,1987, now U.S. Pat. No. 4,757,081.

SUMMARY OF THE INVENTION:

This invention relates to new 4(1H)-pyridinone derivatives, and moreparticularly, new 1,2,6-triphenyl-substituted 4(1H)-pyridinonederivatives which are useful as new compounds or agents having improvedfungicidal activities. This invention also relates to a fungicidalcomposition containing said new 4(1H)-pyridinone derivatives as activeingredient. This invention further relates to processes for theproduction of said new 4(1H)-pyridinone derivatives.

An article of the "Synthetic Communications" 13(5), 411-417 (1983)describes a process for the production of 1,2,6-triphenyl-substituted4(1H)-pyridinone derivatives by reactions between ketimines and ethylphenylpropionate, and this article discloses some examples of the1,2,6-triphenyl-substituted 4(1H)-pyridinone derivatives produced, whichare merely described there to be interesting as intermediate compoundsfor synthetic production of other, final products. On the other hand,Japanese patent application first publication "Kokai" No. 65871/81discloses 1-phenyl-2,6-dimethyl-4(1H)-pyridinone derivatives. It alsocontains a disclosure to the effect that these derivatives are not onlyeffective for cucumber powdery mildew (Sphaerotheca fuliginea) but alsouseful as slime control agents. Similarly, Japanese patent applicationfirst publication "Kokai" No. 102504/80 discloses2,6-diphenyl-4(1H)-pyridinone and contains a description to the effectthat this compound is effective for rice blast (Pyricularia oryzae) andcucumber anthracnose (Colletotrichum lagenarium). 3-Substituted phenyl-or 3,5-disubstituted phenyl-4 -pyridinone derivatives are also disclosedin Japanese patent application second publication "Kokoku" No. 350/85and No. 351/85, and these compounds have activities as herbicides but nodescription is given there as to their fungicidal effects.

The above article in the "Synthetic Communication" does not describeanything about the biological activities of the compounds disclosedthere. In order to provide a novel, agricultural and horticulturalfungicide more useful than the known compounds described in theabove-mentioned publications, we, the present inventors, have paid ourattention on the 1,2,6-triphenyl-substituted 4(1H)-pyridinonederivatives and its skeleton structure and have carried out extensiveinvestigations to provide their new 3-substituted derivatives. As aresult, we have now succeeded to synthesize new compounds of thisinvention. It has also been found that the new compounds of thisinvention have improved and excellent activities as agricultural andhorticultural fungicides, leading to completion of this invention.

DETAILED DESCRIPTION OF THE INVENTION

According to a first and broadest aspect of this invention, there isprovided as new compounds 4(1H)-pyridinone derivatives represented bythe general formula: ##STR1## wherein X, Y and Z are the same ordifferent and are independently a halogen atom, a nitro group, a cyanogroup, a hydroxy group, aldehyde group (--CHO), an alkyl group, ahalogen-substituted alkyl group, a cyanoalkyl group, a hydroxyalkylgroup, an alkoxyalkyl group, an alkoxy group, a halogen-substitutedalkoxy group, an alkoxyalkoxy group, an alkenyl group, an alkenyloxygroup, an alkynyl group, an alkynyloxy group, an alkanoyl group,preferably formyl or acetyl, an alkanoyloxy group, preferably acetyloxy,a phenyl group, a phenoxy group, a carbamoyl group, an alkylcarbamoyloxygroup, a carboxyl or carboxylate group of the formula --COOR¹ where R¹is a hydrogen atom or an alkyl group, or a substituted or unsubstitutedamino group of the formula ##STR2## where R² and R³ are the same ordifferent and are each a hydrogen atom, a lower alkyl group, preferablymethyl, or an alkanoyl group; or X, Y and Z are independently a group ofthe formula --(O)_(p) --S--R⁴ where R⁴ is an alkyl group and p is aninteger of 0 to 3; or X, Y and Z are independently a trimethylene groupor a methylene-dioxo group bonded to and bridging between the adjacenttwo carbon atoms of the benzene ring to which X, Y or Z is linking sothat X, y or Z taken together with said two adjacent two carbon atoms ofthe benzene ring forms a 5-membered ring.

l, m and n are independently an integer of 0 to 5, R is a halogen atom,a cyano group, an alkyl group, a halogen-substituted alkyl group, analkoxy group, an alkenyl group, an alkynyl group, a phenyl group, abenzyl group, a trimethylsilylethynyl group, a carboxyl or carboxylategroup of the formula --COOR¹ where R¹ is as defined above, or asubstituted methyl group of the formula --CH₂ OR⁵ wherein R⁵ is ahydrogen atom, an alkyl group or a benzoyl group,

A is an oxygen atom or a sulfur atom, provided that when R is methyl andA is an oxygen atom, l, m and n do not denote zero simultaneously; andprovided that when R and X are each a methyl group, A is an oxygen atomand l is l, m and n do not denote zero simultaneously, and a salt of thecompound of the formula (I) above.

The compound of the formula (I) according to this invention may also beconverted into their salts with an acid or a cation.

Further, the compounds of this invention may be in the form of such atautomer as indicated below. ##STR3##

In the compounds of formula (I) according to this invention, R maypreferably be an alkyl group, particularly a (C₁ -C₆) alkyl group, or ahalogen atom, a cyano group or a carboxyl or carboxylate group of theformula --COOR¹ where R¹ is a hydrogen atom or an alkyl group. Morepreferably, R is a (C₁ -C₄) alkyl group, a chlorine atom or a bromineatom.

In the compounds of formula (I), X, Y and Z may preferably be the sameor different and are independently an alkyl group, an alkoxy group, ahalogen-substituted alkyl group, an alkoxy group, a halogen-substitutedalkoxy group, a halogen group, nitro group, cyano group, an alkenylgroup, an alkenyloxy group, an alkynyl group or an alkynyloxy group, orX, Y and Z are independently a trimethylene group or a methylene-dioxogroup bonded to and bridging between the adjacent two carbon atoms ofthe benzene ring to which X, Y or Z is linking so that, X, Y or Z takentogether with said two carbon atoms of the benzene ring forms a5-membered ring; l, m and n are independently an integer of 0 to 5; andA is an oxygen atom or a sulfur atom.

In the compounds of formula (I), it is preferred that the sum of l, mand n is equal to 2 or greater than 2.

In the compounds of formula (I), two or more groups may be present foreach of the groups X, Y and X and they are the same or different fromeach other in their nature.

In the compounds of formula (I), it is preferred that X is a halogenatom or an alkoxy group or a combination of halogen atom(s) and alkoxygroup(s); Y is a halogen atom or an alkoxy group or a combination ofhalogen atom(s) and alkoxy group(s); and Z is a halogen atom or analkoxy group or a combination of halogen atom(s) and alkoxy group(s).

In the compounds of formula (I), one, two or three groups for X may bepresent therein and may preferably be positioned at the 2-position, the3-position, the 2- and 4-positions, the 2- and 5-positions, the 3- and5-positions or the 2-, 3- and 5-positions of the benzene ring to whichthe group(s) X is or are linking.

In the compound of the general formula (I) according to this invention,an alkyl group as represented by the substitutents X, Y, Z, R, R¹, R⁴and R⁵, as well as a cycloalkyl group occasionally present in thesessubstituents X, Y, Z and others may be an alkyl group containing 1 to 6carbon atoms, preferably an alkyl group containing 1 to 4 carbon atoms.The alkyl group may include a cycloalkyl group such as cyclopentyl.Suitable examples of an alkyl group includes methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl. The halogengroup includes bromine, chlorine, flourine and iodine.

According to particular embodiments of the first aspect of thisinvention, there are provided the following four types of the compounds:

(A) A compound represented by the general formula (Ia): ##STR4## whereinX^(a) is a halogen atom, a nitro group, a cyano group, a hydroxy group,an alkyl group, a halogen-substituted alkyl group, a cyanoalkyl group, ahydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, ahalogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenylgroup, an alkenyloxy group, an alkynyl group, an alkynyloxy group, analkanoyl group, an alkanoyloxy group, a phenyl group a phenoxy group, acarbamoyl group, an alkylcarbamoyloxy group, a carboxyl or carbooxylategroup of the formula --COOR¹ where R¹ is a hydrogen atom or an alkylgroup, or a substituted or unsubstituted amino group of the formula##STR5## where R² and R³ are the same or different and are each ahydrogen atom, a lower alkyl group, or an alkanoyl group; or X^(a) is agroup of the formula --(O)_(p) --S--R⁴ where R⁴ is an alkyl group an pis an integer of 0 to 3; or X^(a) is a trimethylene group or amethylene-dioxo group bonded to and bridging between the adjacent twocarbon atoms of the benzene ring to which X^(a) is linking so that X^(a)taken together with said two adjacent two carbon atoms of the benzenering forms a 5-membered ring;

Y^(a) is a halogen atom, a nitro group, a cyano group, a hydroxy group,an alkyl group, a halogen-substituted alkyl group, a hydroxyalkyl group,an alkoxyalkyl group, an alkoxy group, a halogen-substituted alkoxygroup, an alkoxyalkoxy group, an alkenyl group, an alkenyloxy group, analkynyl group, an alkynyloxy group, an alkanoyl group, an alkanoyloxygroup, a carbamoyl group, an alkylcarbamoyloxy group, a carboxyl orcarboxylate group of the formula --COOR¹ where R¹ is a hydrogen atom oran alkyl group, or Y^(a) is a group of the formula --(O)_(p) --S--R⁴where R⁴ is an alkyl group and p is an integer of 0 to 3; or Y^(a) is atrimethylene group or a methylene-dioxo group bonded to and bridgingbetween the adjacent two carbon atoms of the benzene ring to which Y^(a)is linking so that Y^(a) taken together with said two adjacent twocarbon atoms of the benzene ring forms a 5-membered ring,

Z^(a) is a halogen atom, a nitro group, a cyano group, a hydroxy group,aldehyde group (--CHO), an alkyl group, a halogen-substituted alkylgroup, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, ahalogen-substituted alkoxy group, an alkoxyalkoxy group, an alkenylgroup, an alkenyloxy group, an alkynyl group, an alkynyloxy group, analkanoyl group, an alkanoyloxy group, preferably acetyloxy, a carbamoylgroup, an alkylcarbamoyloxy group, a carboxyl or carboxylate group ofthe formula --COOR¹ where R¹ is a hydrogen atom or an alkyl group, orZ^(a) is a group of the formula --(O)_(p) --S--R⁴ is an alkyl group andp is an integer of 0 to 3; or Z^(a) is a trimethylene group or amethylene-dioxo group bonded to and bridging between the adjacent twocarbon atoms of the benzene ring to which Z^(a) is linking so that Z^(a)taken together with said two adjacent two carbon atoms of the benzenering forms a 5-membered ring, s is an integer of zero, 1, 2 or 3; t isan integer of zero, 1 or 2; and r is zero, 1 or 2.

R^(a) is a halogen atom, a cyano group, an alkyl group, ahalogen-substituted alkyl group, an alkoxy group, an alkenyl group, analkynyl group, a phenyl group, a benzyl group, a trimethylsilylethynylgroup, a carboxyl or carboxylate group of the formula --COOR¹ where R¹is as defined above, or a substituted methyl group of the formula --CH₂OR⁵ wherein R⁵ is a hydrogen atom, an alkyl group or a benzoyl group,provided that when R^(a) is methyl, s, t and r do not denote zerosimultaneously.

(B) A compound represented by the general formula ##STR6## wherein X^(b)is a halogen atom or an alkoxy group or a combination of halogen atom(s)and alkoxy group(s); Y^(b) is a halogen atom, especially chlorine orflourine, or an alkoxy group and Z^(b) is a halogen atom, especiallyflourine,

s is an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; andr is an integer of zero, 1 or 2.

R^(b) is an alkyl group or a halogen atom, especially chlorine orflourine, provided that when R^(b) is methyl, s, t, and r do not denotezero simultaneously.

(C) A compound represented by the general formula ##STR7## wherein X, Yand Z are the same or different and are independently a halogen atom, analkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group oran alkynyloxy group,

l, m and n are independently an integer of 0 to 5,

R is an alkyl group or a halogen-substituted alkyl group.

(D) A compound represented by the general formula ##STR8## wherein X^(c)is an alkyl group; Y^(c) is a halogen atom, especially chlorine orflourine, an alkyl group, or an alkoxy group; and Z^(c) is a halogenatom, especially flourine,

s in an integer of zero, 1, 2 or 3; t is an integer of zero, 1 or 2; andr is an integer of zero, 1 or 2.

R^(c) is an alkyl group or a halogen atom, especially chlorine orflourine, provided that when R^(c) is methyl, s, t, and r do not denotezero simultaneously, and provided that t and r do not denote zerosimultaneously.

Particular examples of the compounds of this invention represented bythe general formula (I) will next be shown in Table 1a-Table 1d below.Compound numbers given in these Tables will be referred to in thesubsequent descriptions.

                                      TABLE 1a                                    __________________________________________________________________________     ##STR9##                                                                     Com-                                                                          pound                                           Melting                       No. Xl        Ym        Zn        A R           point(°C.)             __________________________________________________________________________    1   2-Cl      H         H         O CH.sub.3    228-231                       2   2-Cl      "         "         " "           229-231                       3   3-Cl      "         "         " "           219-221                       4   4-Cl      "         "         " "           268-270                       5   2-F       "         "         " "           221-225                       6   3-F       "         "         " "           243-246                       7   4-F       "         "         " "           256-259                       8   2-Br      "         "         " "           201-203                       9   2-I       "         "         " "           219-222                       10  2-C.sub.2 H.sub.5                                                                       "         "         " "           230-234                       11  2-C.sub.3 H.sub.7i                                                                      "         "         " "           233-236                       12  4-C.sub.3 H.sub.7i                                                                      "         "         " "           282-284                       13  4-C.sub.4 H.sub.9n                                                                      "         "         " "           150-151                       14  4-C.sub.4 H.sub.9t                                                                      "         "         " "           255-257                       15  2-OCH.sub.3                                                                             "         "         " "           179-181                       16  3-OCH.sub.3                                                                             "         "         " "           183-185                       17  4-OCH.sub.3                                                                             H         H         O CH.sub.3    237-239                       18  2-OC.sub.2 H.sub.5                                                                      "         "         " "           179-182                       19  3-OC.sub.2 H.sub.5                                                                      "         "         " "           206-209                       20  4-OC.sub.2 H.sub.5                                                                      "         "         " "           205-208                       21  2-OC.sub.3 H.sub.7i                                                                     "         "         " "           177-180                       22  3-OC.sub.3 H.sub.7i                                                                     "         "         " "           152-154                       23  4-OC.sub.3 H.sub.7i                                                                     "         "         " "           222-225                       24  2-COOCH.sub. 3                                                                          "         "         " "           227-229                       25  2-COOC.sub.2 H.sub.5                                                                    "         "         " "           208-211                       26  3-COOC.sub.2 H.sub.5                                                                    "         "         " "           196-198                       27  4-COOC.sub.2 H.sub.5                                                                    "         "         " "           202-204                       28  2-OH      "         "         " "           >300                          29  3-OH      "         "         " "           >300                          30  4-OH      "         "         " "           >300                          31                                                                                 ##STR10##                                                                              "         "         " "           199-203                       32  2-NO.sub.2                                                                              "         "         " "           223-225                       33  3-NO.sub.2                                                                              "         "         " "           260-262                       34  4-NO.sub.2                                                                              "         "         " "           271-273                       35  2-CN      "         "         " "           218-222                       36  3-CN      "         "         " "           257-259                       37  4-CN      "         "         " "           285-291                       38  2-NH.sub.2                                                                              "         "         " "           >300                          39  3-NH.sub.2                                                                              "         "         " "           273-277                       40  4-NH.sub.2                                                                              "         "         " "           >300                          41  2-NHCH.sub.3                                                                            H         H         O CH.sub.3    291-293                       42                                                                                 ##STR11##                                                                              "         "         " "           228-233                       43  2-SCH.sub.3                                                                             "         "         " "           228-231                       44  3-SCH.sub.3                                                                             "         "         " "           198-201                       45  4-SCH.sub.3                                                                             "         "         " "           237-238                       46                                                                                 ##STR12##                                                                              "         "         " 250-253                                   47                                                                                 ##STR13##                                                                              "         "         " "           No measurable                 48                                                                                 ##STR14##                                                                              "         "         " "           242-244                       49  2-SO.sub.2 CH.sub.3                                                                     "         "         " "           279-281                       50  3-SO.sub.2 CH.sub.3                                                                     "         "         " "           246-248                       51  4-SO.sub.2 CH.sub.3                                                                     "         "         " "           222-225                       52  2-CH.sub.2 CHCH.sub.2                                                                   "         "         " "           201-204                       53  2-CF.sub.3                                                                              "         "         " "           259-261                       54  3-CF.sub.3                                                                              "         "         " "           235-237                       55  4-CF.sub.3                                                                              "         "         " "           234-237                       56  3-CH.sub.2 OCH.sub.3                                                                    "         "         " "           155-156                       57  2-COCH.sub.3                                                                            "         "         " "                                                                                          ##STR15##                    58  3-COCH.sub.3                                                                            "         "         " "           201-203                       59  2-OCH.sub.2 CHCH.sub.2                                                                  "         "         " "           152-155                       60  3-OCH.sub.2 CHCH.sub.2                                                                  "         "         " "           170-171                       61  4-OCH.sub.2 CHCH.sub.2                                                                  "         "         " "           197-198                       62  2-CCH     H         H         O CH.sub.3    187-190                       63  3-C CH    "         "         " "           241-245                       64  4-CCH     "         "         " "           >300                          65  2-OCHF.sub.2                                                                            "         "         " "           196-200                       66  3-OCHF.sub.2                                                                            "         "         " "           167-169                       67  2-OC.sub.4 H.sub.9n                                                                     "         "         " "           141-144                       68  3-OC.sub.4 H.sub.9n                                                                     "         "         " "           121-123                       69  4-OC.sub.4 H.sub.9n                                                                     "         "         " "           130-134                       70  2-CH.sub.2 CN                                                                           "         "         " "           >300                          71  4-OCF.sub.3                                                                             "         "         " "           235-237                       72  4-OCF.sub.2 CF.sub.2 H                                                                  "         "         " "           151-154                       73                                                                                 ##STR16##                                                                              "         "         " "           236.5-237                     74                                                                                 ##STR17##                                                                              "         "         " "           234-235                       75  3-OCH.sub.2 CCH                                                                         "         "         " "           166-169                       76  2,3-Cl.sub.2                                                                            "         "         " "                                                                                          ##STR18##                    77  2,4-Cl.sub.2                                                                            "         "         " "           257-260                       78  2,5-Cl.sub.2                                                                            "         "         " "           269-271                       79  2,6-Cl.sub.2                                                                            "         "         " "           232-235                       80  3,4-Cl.sub.2                                                                            "         "         " "           233-235                       81  3,5-Cl.sub.2                                                                            "         "         " "           253-255                       82  2,3-(CH.sub.3).sub.2                                                                    "         "         " "           212-214                       83  2,4-(CH.sub.3).sub.2                                                                    "         "         " "           217-220                       84  2,5-(CH.sub.3).sub.2                                                                    "         "         " "           268-269                       85  2,6-(CH.sub.3).sub.2                                                                    "         "         " "           197-200                       86  3,4-(CH.sub.3).sub.2                                                                    H         H         O CH.sub.3    222-225                       87  3,5-(CH.sub.3).sub. 2                                                                   "         "         " "           268-271                       88  2,3-(OCH.sub.3).sub.2                                                                   "         "         " "           198-199                       89  2,4-(OCH.sub.3).sub.2                                                                   "         "         " "           222-225                       90  2,5-(OCH.sub.3).sub.2                                                                   "         "         " "           197-199                       91  2,6-(OCH.sub.3).sub.2                                                                   "         "         " "           185-187                       92  3,4-(OCH.sub.3).sub.2                                                                   "         "         " "           230-232                       93  3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           232-236                       94  2,3-F.sub.2                                                                             "         "         " "           210-212                       95  2,4-F.sub.2                                                                             "         "         " "           260-261                       96  2,5-F.sub.2                                                                             "         "         " "           216-218                       97  2,6-F.sub.2                                                                             "         "         " "           219-221                       98  3,4-F.sub.2                                                                             "         "         " "           228-229                       99  3,5-F.sub.2                                                                             "         "         " "           268-269                       100 2,3-Br.sub.2                                                                            "         "         " "           --                            101 2,4-Br.sub.2                                                                            "         "         " "           256-259                       102 2,5-Br.sub.2                                                                            "         "         " "           285-287                       103 2,6-Br.sub.2                                                                            "         "         " "           --                            104 2-Cl,6-CH.sub.3                                                                         "         "         " "           189-191                       105 2-Cl,4-NO.sub.2                                                                         "         "         " "           212-214                       106 2-Cl,5-NO.sub.2                                                                         "         "         " "           277-279                       107 2-Cl,4-Br "         "         " "           252-255                       108 2-Cl,5-CF.sub.3                                                                         "         "         " "           256-258                       109 2-Cl,5-CH.sub.3                                                                         "         "         " "           240-240.5                     110 2-CH.sub.3,3-Cl                                                                         "         "         " "           244-246                       111 2-CH.sub.3,4-Cl                                                                         H         H         O CH.sub.3    240-242                       112 2-CH.sub.3,5-Cl                                                                         "         "         " "           >300                          113 2-CH.sub.3,4-Br                                                                         "         "         " "           235-237                       114 2-CH.sub.3,5-F                                                                          "         "         " "           277.5-278                     115 2-NO.sub.2,4-Cl                                                                         "         "         " "           220-223                       116 2-Br,4-CH.sub.3                                                                         "         "         " "           226-229                       117 2-F,5-NO.sub.2                                                                          "         "         " "           220-222                       118 2-OCH.sub.3,5-Cl                                                                        "         "         " "           229-232                       119 2-OCH.sub.3,5-CH.sub.3                                                                  "         "         " "           215-216                       120 2-CF.sub.3,4-Cl                                                                         "         "         " "           241-243                       121 2-CN,4-Cl "         "         " "                                                                                          ##STR19##                    122 3-Cl,4-CH.sub.3                                                                         "         "         " "           226-228                       123 3-Cl,4-F  "         "         " "           224-225                       124 3-NO.sub.2,4-F                                                                          "         "         " "           225-227                       125 3-NO.sub.2,4-Cl                                                                         "         "         " "           247-248                       126 3-CF.sub.3,4-Cl                                                                         "         "         " "           231-232                       127 3-CF.sub.3,4-OCH.sub.3                                                                  "         "         " "           205-208                       128 3-CH.sub.3,4-Br                                                                         "         "         " "           225-227                       129 2-CH.sub.3,5-OCH.sub.3                                                                  "         "         " "           228-229                       130 2-CH.sub.3,3-OCH.sub.3                                                                  "         "         " "           231-233                       131 2-CH.sub.3,4-NO.sub.2                                                                   "         "         " "           248-249                       132 2-OCH.sub.3,4-NO.sub.2                                                                  "         "         " "           229-231                       133 2-OCH.sub.3,5-NO.sub.2                                                                  "         "         " "           224-225                       134 2-NO.sub.2,4-OCH.sub.3                                                                  "         "         " "           209-210                       135 2-Cl,5-OCH.sub.3                                                                        "         "         " "           224-225                       136 2-OCH.sub.3,6-CH.sub.3                                                                  H         H         O CH.sub.3    163-165                       137 2-CH.sub.3,3-F                                                                          "         "         " "           267-268                       138 2-NO.sub.2,4-CH.sub.3                                                                   "         "         " "           253-255                       139 2-NO.sub.2,5-Cl                                                                         "         "         " "           212-214                       140 2-CH.sub.3,5-NO.sub.2                                                                   "         "         " "           >300                          141 3,5-(OH).sub.2                                                                          "         "         " "           >300                          142 3,5-(OCHF.sub.2).sub.2                                                                  "         "         " "           179-181                       143 3,5-(OC.sub.2 H.sub.5).sub.2                                                            "         "         " "           156-158                       144 3,5-(On-C.sub.3 H.sub. 7).sub.2                                                         "         "         " "           156-158                       145 2-CH.sub.3,4-OCH.sub.3                                                                  "         "         " "           195-197                       146 2-OCH.sub.3,4-CH.sub.3                                                                  "         "         " "           217-219                       147 2-Cl,4-CH.sub.3                                                                         "         "         " "           222-224                       148 2-Cl,3-OCH.sub.3                                                                        "         "         " "           226-227                       149 2,4-Cl.sub.2,3-CH.sub.3                                                                 "         "         " "           237-238                       150 3,4,5-(OCH.sub.3).sub.3                                                                 "         "         " "           254-255                       151 2,4-Cl.sub.2,5-OC.sub.3 H.sub.7i                                                        "         "         " "           205-206                       152 2,3,4-Cl.sub.3                                                                          "         "         " "           257-258                       153 2,4-F.sub.2,3,5-Cl.sub.2                                                                "         "         " "           243-245                       154 2-Cl,3,5-(OCH.sub.3).sub.2                                                              "         "         " "           262-263                       155 2,3,4,5,6-F.sub.5                                                                       "         "         " "           192-194                       156 2,3,4,5-Cl.sub.4                                                                        "         "         " "           294-296                       157 2,3,4,6-Cl.sub.4                                                                        "         "         " "           --                            158 2,3,5,6-F.sub.4                                                                         "         "         " "           220-222                       159 2-Cl      "         "         " C.sub.2 H.sub.5                                                                           163-166                       160 "         "         "         " Cl          230-233                       161 2-Br      H         H         O Cl          238-241                       162 3-Cl      "         "         " "           276-279                       163 4-Cl      "         "         " "           >300                          164 2-F       "         "         " "           227-229                       165 2-I       "         "         " "           238-239                       166 2-CH.sub.3                                                                              "         "         " "           266-268                       167 3-CH.sub.3                                                                              "         "         " "           271-273                       168 4-CH.sub.3                                                                              "         "         " "           292-296                       169 2-OCH.sub.3                                                                             "         "         " "           208-209                       170 3-OCH.sub.3                                                                             "         "         " "           250-251                       171 4-OCH.sub.3                                                                             "         "         " "           266-267                       172 2-NO.sub.2                                                                              "         "         " "           250-252                       173 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           275-276                       174 "         "         "         " C.sub.2 H.sub.5                                                                           166-167                       175 2-Cl,5-OCH.sub.3                                                                        "         "         " "           175-176                       176 H         2-Cl      "         " CH.sub.3    221-225                       177 "         3-Cl      "         " "           225-227                       178 "         4-Cl      "         " "           209-212                       179 "         2-F       "         " "           177-180                       180 "         3-F       "         " "           226-228                       181 "         4-F       "         " "           239-244                       182 "         2-Br      "         " "           240-241                       183 "         2-Br      "         " "           236-238                                                                       (hydrochloride)               184 "         3-Br      "         " "           237-239                       185 "         4-Br      "         " "           203-206                       186 H         2-I       H         O CH.sub.3    239-241                       187 "         2-CH.sub.3                                                                              "         " "           194-196                       188 "         3-CH.sub.3                                                                              "         " "           209-211                       189 "         4-CH.sub.3                                                                              "         " "           243-246                       190 "         2-C.sub.3 H.sub.7i                                                                      "         " "           206-209                       191 "         4-C.sub.3 H.sub.7i                                                                      "         " "           194-197                       192 "         2-OCH.sub.3                                                                             "         " "           200-202                       193 "         3-OCH.sub.3                                                                             "         " "           201-204                       194 "         4-OCH.sub.3                                                                             "         " "           183-185                       195 "         3-OC.sub.2 H.sub.5                                                                      "         " "           146-149                       196 "         4-OC.sub.2 H.sub.5                                                                      "         " "           189-193                       197 "         3-OC.sub.3 H.sub.7n                                                                     "         " "           137-139                       198 "         4-OC.sub.3 H.sub.7n                                                                     "         " "           165-168                       199 "         2-OC.sub.3 H.sub.7i                                                                     "         " "           212-214                       200 "         3-OC.sub.3 H.sub.7i                                                                     "         " "           161-163                       201 "         4-OC.sub.3 H.sub.7i                                                                     "         " "           198-201                       202 "         3-COOC.sub.2 H.sub.5                                                                    "         " "           141-144                       203 "         4-COOC.sub.2 H.sub.5                                                                    "         " "           99-103                        204 "         2-OH      "         " "           >300                          205 "         3-OH      "         " "           >300                          206 "         4-OH      "         " "           >300                          207 "                                                                                        ##STR20##                                                                              "         " "           182-184                       208 "                                                                                        ##STR21##                                                                              "         " "           213-216                       209 "         3-CN      "         " "           262-265                       210 H         4-CN      H         O CH.sub.3    240-243                       211 "         2-SCH.sub.3                                                                             "         " "           199-202                       212 "         4-SCH.sub.3                                                                             "         " "           200-203                       213 "         2-CF.sub.3                                                                              "         " "           238-241                       214 "         3-CF.sub.3                                                                              "         " "           221-223                       215 "         4-CF.sub.3                                                                              "         " "           209-211                       216 "         2-OCH.sub.2 CHCH.sub.2                                                                  "         " "           145-148                       217 "         4-OCH.sub.2 CHCH.sub.2                                                                  "         " "           196-199                       218 "         2-OCH.sub.2 CCH                                                                         "         " "           211-213                       219 "         4-OCH.sub.2 CCH                                                                         "         " "           168-170                       220 "         2-OCHF.sub.2                                                                            "         " "           162-164                       221 "         3-COOH    "         " "           291-294                       222 "         2-C.sub.2 H.sub.5                                                                       "         " "           --                            223 "         2-C.sub.3 H.sub.7n                                                                      "         " "           --                            224 "         4-OCH.sub.2 OCH.sub.3                                                                   "         " "           188-190                       225 "         2,3-Cl.sub.2                                                                            "         " "           274-278                       226 "         2,4-Cl.sub.2                                                                            "         " "           183-185                       227 "         2,5-Cl.sub.2                                                                            "         " "           264-267                       228 "         2,6-Cl.sub.2                                                                            "         " "           --                            229 "         3,4-Cl.sub.2                                                                            "         " "           188-191                       230 "         3,5-Cl.sub.2                                                                            "         " "           274-277                       231 "         2,3-(CH.sub.3).sub.2                                                                    "         " "           250-254                       232 "         2,4-(CH.sub.3).sub.2                                                                    "         " "           134-136                       233 "         2,5-(CH.sub.3).sub.2                                                                    "         " "           215-217                       234 "         2,6-(CH.sub.3).sub.2                                                                    "         " "           --                            235 H         3,4-(CH.sub.3).sub.2                                                                    H         O CH.sub.3    165-166                       236 "         3,5-(CH.sub.3).sub.2                                                                    "         " "           237-239                       237 "         2,3-(OCH.sub.3).sub.2                                                                   "         " "           230-235                       238 "         2,4-(OCH.sub.3).sub.2                                                                   "         " "           192-194                       239 "         2,5-(OCH.sub.3).sub.2                                                                   "         " "           242-244                       240 "         2,6-(OCH.sub.3).sub.2                                                                   "         " "           --                            241 "         3,4-(OCH.sub.3).sub.2                                                                   "         " "           210-214                       242 "         3,5-(OCH.sub.3).sub.2                                                                   "         " "           212-214                       243 "         2,3-F.sub.2                                                                             "         " "           165-167                       244 "         2,4-F.sub.2                                                                             "         " "           213-214                       245 "         2,5-F.sub.2                                                                             "         " "           222-224                       246 "         2,6-F.sub.2                                                                             "         " "           221-222                       247 "         3,4-F.sub.2                                                                             "         " "           202-203                       248 "         3,5-F.sub.2                                                                             "         " "           205-206                       249 "         4-OCHF.sub.2                                                                            "         " "           165-166                       250 "                                                                                        ##STR22##                                                                              "         " "           232-235                       251 "         2-Cl,4-OCH.sub.3                                                                        "         " "           205-206                       252 "         H         2-Cl      " "           201-204                       253 "         "         3-Cl      " "           234-236                       254 "         "         4-Cl      " "           173-175                       255 "         "         2-F       " "           219-222                       256 "         "         3-F       " "           204-206                       257 "         "         4-F       " "           184-186                       258 "         "         2-Br      " "           206-209                       259 H         H         2-I       O CH.sub.3    226-229                       260 "         "         2-CH.sub.3                                                                              " "           188-191                       261 "         "         3-CH.sub.3                                                                              " "           236-238                       262 "         "         4-CH.sub.3                                                                              " "           212-215                       263 "         "         2-C.sub.2 H.sub.5                                                                       " "           --                            264 "         "         2-C.sub.3 H.sub.7i                                                                      " "           224-228                       265 "         "         2-C.sub.4 H.sub.9n                                                                      " "           --                            266 "         "         2-OCH.sub.3                                                                             " "           192-194                       267 "         "         3-OCH.sub.3                                                                             " "           201-204                       268 "         "         4-OCH.sub.3                                                                             " "           185-188                       269 "         "         2-OC.sub.2 H.sub.5                                                                      " "           175-179                       270 "         "         2-OC.sub.3 H.sub.7n                                                                     " "           166-171                       271 "         "         2-OC.sub.3 H.sub.7i                                                                     " "           165-168                       272 "         "         3-COOC.sub.2 H.sub.5                                                                    " "           no                                                                            measurable                    273 "         "         4-COOC.sub.2 H.sub.5                                                                    " "           161-165                       274 "         "         2-OH      " "           >300                          275 "         "         3-OH      " "           >300                          276 "         "         4-OH      " "           262-268                       277 "         "                                                                                        ##STR23##                                                                              " "           115-122                       278 "         "         3-NO.sub.2                                                                              " "           210-211                       279 "         "         4-NO.sub.2                                                                              " "           213-216                       280 "         "         2-CN      " "           261-266                       281 "         "         3-CN      " "           211-214                       282 "         "         4-CN      " "           229-233                       283 H         H         2-SCH.sub.3                                                                             O CH.sub.3    189-195                       284 "         "         2-CH.sub.2 Cl                                                                           " "           167-170                       285 "         "         2-CF.sub.3                                                                              " "           200-205                       286 "         "         3-CF.sub.3                                                                              " "           212-215                       287 "         "         2-CH.sub.2 OCH.sub.3                                                                    " "           172-176                       288 "         "         2-CH.sub.2 OC.sub.2 H.sub.5                                                             " "           121-124                       289 "         "         2-OCH.sub.2 CF.sub.3                                                                    " "           191-194                       290 "         "         2-COCH.sub.3                                                                            " "           --                            291 "         "         2-OCH.sub.2 CHCH.sub.2                                                                  " "           171-174                       292 "         "         2-OCH.sub.2 CCH                                                                         " "           182-185                       293 "         "         2-OCHF.sub.2                                                                            " "           163-165                       294 "         "         2-COOH    " "           --                            295 "         "         3-COOH    " "           >300                          296 "         "         4-COOH    " "           >293                          297 "         "         2-CH.sub.2 OH                                                                           " "           254-257                       298 "         "         2-CHO     " "           169-173                       299 "         "         2-SO.sub.2 CH.sub.3                                                                     " "           >300                          300 "         "                                                                                        ##STR24##                                                                              " "           272-275                       301 "         "         2-OSO.sub.2 CH.sub. 3                                                                   " "           209-214                       302 "         "         2-O.sub.2 CNHCH.sub.3                                                                   " "           >300                          303 "         "         2-OCH.sub.2 OCH.sub.3                                                                   " "           178-181                       304 "         "         2,3-Cl.sub.2                                                                            " "           183-191                       305 "         "         2,4-Cl.sub.2                                                                            " "           218-221                       306 "         "         2,5-Cl.sub.2                                                                            " "           >300                          307 "         "         2,6-Cl.sub.2                                                                            " "           151-154                       308 H         H         3,4-Cl.sub.2                                                                            O CH.sub.3    234-236                       309 "         "         2,3-(CH.sub.3).sub.2                                                                    " "           206-208                       310 "         "         2,4-(CH.sub.3).sub.2                                                                    " "           175-178                       311 "         "         2,5-(CH.sub.3).sub.2                                                                    " "           231-235                       312 "         "         2,6-(CH.sub.3).sub.2                                                                    " "           --                            313 "         "         3,4-(CH.sub.3).sub.2                                                                    " "           212-215                       314 "         "         3,5-(CH.sub.3).sub.2                                                                    " "           283-286                       315 "         "         2,3-F.sub.2                                                                             " "           196-197                       316 "         "         2,4-F.sub.2                                                                             " "           206-207                       317 "         "         2,5-F.sub.2                                                                             " "           244-247                       318 "         "         2,6-F.sub.2                                                                             " "           235-238                       319 "         "         3,4-F.sub.2                                                                             " "           188-189                       320 "         "         3,5-F.sub.2                                                                             " "           234-236                       321 "         "         3,5-(OCH.sub.3).sub.2                                                                   " "           205-206                       322 "         "         2,4-(OCH.sub.3).sub.2                                                                   " "           253-257                       323 "         "         3,4-(OCH.sub.3).sub.2                                                                   " "           212-215                       324 "         "         2-OC.sub.2 H.sub.5,4-F                                                                  " "           236-237                       325 "         "         2-OCH.sub.3,5-Cl                                                                        " "           192-197                       326 "         "         3,5-Cl.sub.2                                                                            " "           >300                          327 "         "         2-F,3-OCH.sub.3                                                                         " "           169-172                       328 "         "         2-OCH.sub.3,5-F                                                                         " "           185-186                       329 "         "         2,6-(OCH.sub.3).sub.2                                                                   " "           206-210                       330 "         "         2,3-(OCH.sub.3).sub.2                                                                   " "           239-243                       331 "         "         3,4-(OH).sub.2                                                                          " "           >300                          332 "         "         3,5-(OH).sub.2                                                                          " "           >300                          333 H         H         3,4-(OCHF.sub.2).sub.2                                                                  O CH.sub.3    178-180                       334 "         "         2,5-(OCH.sub.3).sub.2                                                                   " "           242-245                       335 2-Cl      2-Cl      H         " "           205-207                       336 "         "         "         " "           232-234                       337 2-CH.sub.3                                                                              "         "         " "           197-200                       338 "         "         "         " "           227-229                       339 "         "         "         " "           222-225                       340 2-Cl      4-OCH.sub.3                                                                             "         " "           184-188                       341 2-CH.sub.3                                                                              3-OCH.sub.3                                                                             "         " "           212-213                       342 3-CH.sub.3                                                                              "         "         " "           195-196                       343 4-CH.sub.3                                                                              "         "         " "           182-183                       344 2-OCH.sub.3                                                                             "         "         " "           167-169                       345 3-OCH.sub.3                                                                             "         "         " "           153-155                       346 4-OCH.sub.3                                                                             "         "         " "           184-186                       347 2-CH.sub.3                                                                              3-Cl      "         " "           274-275                       348 3-CH.sub.3                                                                              "         "         " "           219-221                       349 4-CH.sub.3                                                                              "         "         " "           206-208                       350 2-OCH.sub.3                                                                             "         "         " "           231-233                       351 3-OCH.sub.3                                                                             "         "         " "           197-198                       352 4-OCH.sub.3                                                                             "         "         " "           206-207                       353 2-Cl      3-OCH.sub.3                                                                             "         " "           212-213                       354 3-Cl      "         "         " "           187-188                       355 4-Cl      "         "         " "           189-191                       356 3-Cl      2-Cl      "         " "           196-198                       357 4-Cl      "         "         " "           233-236                       358 3-CH.sub.3                                                                              2-Cl      H         O CH.sub.3    206-209                       359 4-CH.sub.3                                                                              "         "         " "           210-211                       360 2-OCH.sub.3                                                                             "         "         " "           173-176                       361 3-OCH.sub.3                                                                             "         "         " "           166-170                       362 4-OCH.sub.3                                                                             "         "         " "           186-188                       363 2-COOCH.sub.3                                                                           "         "         " "           180-182                       364 2-F       "         "         " "           207-208                       365 "         "         "         " "           201-203                       366 2-Br      "         "         " "           117-120                       367 "         "         "         " "           192-195                       368 2-NO.sub.2                                                                              "         "         " "           241-242                       369 "         "         "         " "           233-235                       370 3-Cl      4-OCH.sub.3                                                                             "         " "           199-203                       371 4-Cl      "         "         " "           232-234                       372 2-CH.sub.3                                                                              "         "         " "           191-193                       373 3-CH.sub.3                                                                              "         "         " "           187-189                       374 4-CH.sub.3                                                                              "         "         " "           184-186                       375 2-OCH.sub.3                                                                             "         "         " "           248-260                       376 3-OCH.sub.3                                                                             "         "         " "           207-209                       377 4-OCH.sub.3                                                                             "         "         " "           212-214                       378 2-NO.sub.2                                                                              "         "         " "           235-237                       379 4-NO.sub.2                                                                              2-Cl      "         " "           >300                          380 3-NO.sub.2                                                                              "         "         " "           193-195                       381 3-OCH.sub.3                                                                             2-CH.sub.3                                                                              "         " "           145-148                       382 2-Cl      "         "         " "           193-195                       383 4-CH.sub.3                                                                              2-CH.sub.3                                                                              H         O CH.sub.3    203-204                       384 2-NO.sub.2                                                                              "         "         " "           246-248                       385 2,5-F.sub.2                                                                             2-Cl      "         " "           189-191                       386 2,3-Cl.sub.2                                                                            "         "         " "           237-239                       387 3,5-Cl.sub.2                                                                            "         "         " "           221-223                       388 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           226-229                       389 3,5-(OC.sub.2 H.sub.5).sub.2                                                            "         "         " "           195-198                       390 3,5-(OCHF.sub.2).sub.2                                                                  "         "         " "           129-130                       391 3,5-(OH).sub.2                                                                          "         "         " "           >300                          392 3,5-(OCH.sub.3).sub.2                                                                   4-OCH.sub.3                                                                             "         " "           181-183                       393 "         3-Cl      "         " "           209-211                       394 2,5-F.sub.2                                                                             2-CH.sub.3                                                                              "         " "           182-184                       395 2-CH.sub.3,3-Cl                                                                         "         "         " "           230-231                       396 2,3-Cl.sub.2                                                                            "         "         " "           139-141                       397 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           202-203                       398 "         3-OCH.sub.3                                                                             "         " "           207-209                       399 2-NO.sub.2                                                                              "         "         " "           204-208                       400 3,5-(OCH.sub.3).sub.2                                                                   2-OCH.sub.3                                                                             "         " "           196-198                       401 3-OCH.sub.3                                                                             "         "         " "           170-172                       402 4-OCH.sub.3                                                                             "         "         " "           225-227                       403 4-CH.sub.3                                                                              "         "         " "           225-227                       404 2-Cl      "         "         " "           223-226                       405 3-NO.sub.2                                                                              "         "         " "           180-184                       406 "         3-OCH.sub.3                                                                             "         " "           240-244                       407 "         4-OCH.sub.3                                                                             "         " "           255-260                       408 2,5-F.sub.2                                                                             4-OCH.sub.3                                                                             H         O CH.sub.3    220-222                       409 2-Cl,5-OCH.sub.3                                                                        "         "         " "           225-236                       410 3-Cl      3-Cl      "         " "           243-244                       411 4-Cl      "         "         " "           299-300                       412 2,5-F.sub.2                                                                             "         "         " "           230-233                       413 2-NO.sub.2                                                                              "         "         " "           273-275                       414 3-NO.sub.2                                                                              "         "         " "           >300                          415 2-Cl      2-Br      "         " "           218-220                       416 "         "         "         " "           225-227                       417 3-Cl      "         "         " "           214-216                       418 4-CH.sub.3                                                                              "         "         " "           226-229                       419 3-CH.sub.3                                                                              "         "         " "           227-228                       420 2-CH.sub.3                                                                              "         "         " "           197-199                       421 4-Cl      "         "         " "           224-226                       422 2-OCH.sub.3                                                                             "         "         " "           153-156                       423 3-OCH.sub.3                                                                             "         "         " "           147-150                       424 4-OCH.sub.3                                                                             "         "         " "           216-218                       425 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           224-226                       426 2,5-F.sub.2                                                                             "         "         " "           211-214                       427 "         "         "         " "           211-213                       428 2-NO.sub.2                                                                              "         "         " "           220-224                       429 "         "         "         " "           201-204                       430 3-NO.sub.2                                                                              "         "         " "           192-196                       431 2-Cl      2,4-F.sub.2                                                                             "         " "           120-121                       432 "         "         "         " "           198-199                       433 3,5-(OCH.sub.3).sub.2                                                                   2,4-F.sub.2                                                                             H         O CH.sub.3    180-182                       434 "         3,4-F.sub.2                                                                             "         " "           217-218                       435 2-Cl      4-CH.sub.3                                                                              "         " "           230-233                       436 3-OCH.sub.3                                                                             "         "         " "           230-231                       437 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           223-225                       438 2-CH.sub.3                                                                              2-OCH.sub.3                                                                             "         " "           188-191                       439 3-CH.sub.3                                                                              "         "         " "           183-185                       440 2-OCH.sub.3                                                                             "         "         " "           194-197                       441 2-NO.sub.2                                                                              "         "         " "           243-245                       442 3-Cl      "         "         " "           213-215                       443 4-Cl      "         "         " "           245-248                       444 2-Cl      4-Cl      "         " "           218-220                       445 2-Cl,3-OCH.sub.3                                                                        4-OCH.sub.3                                                                             "         " "           222-223                       446 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           202-204                       447 2-F       2-Br      "         " "           220-223                       448 "         "         "         " "           177-179                       449 2,3-Cl.sub.2                                                                            "         "         " "           249-251                       450 2-Cl,5-OCH.sub.3                                                                        "         "         " "           232-235                       451 2-Cl      2-F       "         " "           199-200                       452 "         "         "         " "           203-204                       453 2-F       "         "         " "           190-191                       454 "         "         "         " "           188- 189                      455 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           218-219                       456 3-Cl      4-Cl      "         " "           239-241                       457 4-Cl      "         "         " "           238-240                       458 2-CH.sub.3                                                                              4-Cl      H         O CH.sub.3    254-256                       459 3-CH.sub.3                                                                              "         "         " "           189-190                       460 4-CH.sub.3                                                                              "         "         " "           194-195                       461 2-OCH.sub.3                                                                             "         "         " "           226-228                       462 3-OCH.sub.3                                                                             "         "         " "           257-259                       463 4-OCH.sub.3                                                                             "         "         " "           261-266                       464 2-NO.sub.2                                                                              "         "         " "           238-239                       465 3-NO.sub.2                                                                              "         "         " "           228-229                       466 3,5-(OCH.sub.3).sub.2                                                                   2-Cl,4-OCH.sub.3                                                                        "         " "           223-224                       467 2-CH.sub.3,5-OCH.sub.3                                                                  4-OCH.sub.3                                                                             "         " "           229-231                       468 2-CH.sub.3,3-OCH.sub.3                                                                  "         "         " "           216-218                       469 3,5-(OCH.sub.3).sub.2                                                                   "         "         " C.sub.2 H.sub.5                                                                           170-171                       470 2-Cl,5-OCH.sub.3                                                                        "         "         " "           185-187                       471 2-Cl      H         2-Cl      " CH.sub.3    164-167                       472 "         "         2-F       " "           228-231                       473 "         "         2-OCH.sub.3                                                                             " "           208-210                       474 2,6-F.sub.2                                                                             "         2-Cl      " "           213-215                       475 3-Cl      "         "         " "           234-237                       476 4-Cl      "         "         " "           229-230                       477 2-CH.sub.3                                                                              "         "         " "           187-190                       478 3-CH.sub.3                                                                              "         "         " "           215-217                       479 4-CH.sub.3                                                                              "         "         " "           204-205                       480 2-OCH.sub.3                                                                             "         "         " "           184-189                       481 3-OCH.sub.3                                                                             "         "         " "           182-186                       482 4-OCH.sub.3                                                                             "         "         " "           197-200                       483 2-F       H         2-Cl      O CH.sub.3    188-190                       484 2-CN      "         "         " "           217-219                       485 2-Cl      "         3-NO.sub.2                                                                              " "           291-293                       486 2-NO.sub.2                                                                              "         2-Cl      " "           217-219                       487 3-NO.sub.2                                                                              "         "         " "           195-196                       488 4-NO.sub.2                                                                              "         "         " "           290-295                       489 2,5-F.sub.2                                                                             "         "         " "           231-233                       490 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           239-241                       491 3-Cl      "         2-F       " "           224-226                       492 4-Cl      "         "         " "           255-257                       493 2-CH.sub.3                                                                              "         "         " "           183-185                       494 3-CH.sub.3                                                                              "         "         " "           213-214                       495 4-CH.sub.3                                                                              "         "         " "           204-205                       496 2-OCH.sub.3                                                                             "         "         " "           201-202                       497 3-OCH.sub.3                                                                             "         "         " "           206-207                       498 4-OCH.sub.3                                                                             "         "         " "           225-226                       499 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           226-227                       500 2-Cl      "         4-CH.sub.3                                                                              " "           232-233                       501 3-OCH.sub.3                                                                             "         "         " "           199-201                       502 2,5-F.sub.2                                                                             "         2-F       " "           211-212                       503 2-Cl,5-OCH.sub.3                                                                        "         "         " "           191-192                       504 2-Br      "         "         " "           218-219                       505 2-F       "         "         " "           212-213                       506 2-Cl      "         3-CH.sub.3                                                                              " "           213-215                       507 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           201-203                       508 2-F       H         3-CH.sub.3                                                                              O CH.sub.3    211-214                       509 2,3-Cl.sub.2                                                                            "         2-F       " "           217-218                       510 2-NO.sub.2                                                                              "         "         " "           213-214                       511 H         2-Cl      2-Cl      " "           215-218                       512 "         4-OCH.sub.3                                                                             "         " "           244-246                       513 "         "         2-F       " "           228-231                       514 2-Cl      2-Cl      2-Cl      " "           205-207                       515 2-NO.sub.2                                                                              "         "         " "           189-193                       516 "         "         "         " "           237-245                       517 2-Cl      4-OCH.sub.3                                                                             "         " "           216-217                       518 3,5-(OCH.sub. 3).sub.2                                                                  "         "         " "           185-186                       519 2,5-F.sub.2                                                                             "         "         " "           206-209                       520 2-Cl      "         2-F       " "           204-207                       521 3,5-(OCH.sub.3).sub.2                                                                   "         "         " "           176-178                       522 H         H         H         " Cl          285-287                       523 "         "         "         " Br          274-277                       524 "         "         "         " I           275-277                       525 "         "         "         " C.sub.2 H.sub.5                                                                           173-176                       526 "         "         "         " C.sub.3 Hn  158-160                       527 "         "         "         " C.sub.4 H.sub.9n                                                                          101-103                       528 "         "         "         " C.sub.3 H.sub.7i                                                                          181-184                       529 "         "         "         " CH.sub.2 Cl 214-216                       530 "         "         "         " CH.sub.2 Br no                                                                            measurable                    531 "         "         "         " CH.sub.2 OCH.sub.3                                                                        176-180                       532 "         "         "         " CH.sub.2 OH 196-199                       533 H         H         H         O COOH        257-259                       534 "         "         "         " CN          >300                          535 "         "         "         " OCH.sub.3   188-191                       536 "         "         "         " CF.sub.3    222-225                       537 "         "         "         " COOC.sub.2 H.sub.5                                                                        184-187                       538 "         "         "         " CH.sub.2 CHCH.sub.2                                                                       157-159                       539 "         "         "         "                                                                                ##STR25##  161-164                       540 "         "         "         "                                                                                ##STR26##  210-213                       541 "         "         "         "                                                                                ##STR27##  194-196                       542 2-Cl      "         "         S CH.sub.3    271-275                       543 H         "         "         " "           264-266                       __________________________________________________________________________

                                      TABLE 1b                                    __________________________________________________________________________    Compound                                Melting                               No.   Xl         Ym     Zn         A R  point (°C.)                    __________________________________________________________________________    544   2-Cl,5-OCH.sub.3                                                                         H      3-CH.sub.3 O CH.sub.3                                                                         202-205                               545   2-Cl       4-F    H          " "  235-242                               546   2-F        "      "          " "  247-249                               547   3,5-(OCH.sub.3).sub.2                                                                    "      "          " "  202-204                               548   2-Cl, 5-OCH.sub.3                                                                        "      "          " "  203-206                               549   "          2,4-F.sub.2                                                                          "          " "  184-186                               550   2-CH.sub.3, 4-OCH.sub.3                                                                  4-OCH.sub.3                                                                          "          " "  179-182                               551   2-Cl, 3,5-(OCH.sub.3).sub.2                                                              "      "          " "  230-232                               552   2-Cl                                                                                      ##STR28##                                                                           "          " "  237-239                               553   3,5-(OCH.sub.3).sub.2                                                                    "      "          " "  247-248                               554   H          H      2-CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.3                                                   " "  118-122                               555   2-Cl, 5-OCH.sub.3                                                                        "      2-CH.sub.2 OCH.sub.2 CH.sub.3                                                            " "  183-184                               556   "          2-F    H          " "  223-224                               557   2-Cl, 3,5-(OCH.sub.3).sub.2                                                              H      2-F        " "  237-238                               558   3,5-(OCH.sub.3).sub.2                                                                    2-F    "          " "  193-194                               559   2-Cl, 5-OCH.sub.3                                                                        3-CH.sub.3                                                                           H          " "  212-215                               560   "          2-Cl, 4-OCH.sub.3                                                                    "          " "  209-211                               561   "          "      "          " "  205-206                               562   "          4-CH.sub.3                                                                           "          " "  238-239                               563   2,5-F.sub.2                                                                              "      "          " "  240-243                               564   2,3-Cl.sub.2                                                                             2,4-F.sub.2                                                                          "          " "  165-167                               565   2,3-Cl.sub.2                                                                             2,4-F.sub.2                                                                          H          O CH.sub.3                                                                         225-227                               566   2,5-F.sub.2                                                                              "      "          " "  216-218                               567   "          "      "          " "  212-215                               568   2-Cl       3-Cl   "          " "  256-260                               569   2,3-Cl.sub.2                                                                             "      "          " "  253-255                               570   2-F        "      "          " "  246-248                               571   3,5-(OCH.sub.2 CCH).sub.2                                                                H      "          " "  157-159                               572   2-F        4-Cl   "          " "  235-238                               573   3,5-(OCH.sub.3).sub.2                                                                    "      "          " "                                                                                 ##STR29##                            574   2-Cl, 5-OCH.sub.3                                                                        2-Cl   "          " "                                                                                 ##STR30##                            575   "          "      "          " "  229-230                               576   2-Cl, 3,5-(OCH.sub.3).sub.2                                                              "      "          " "  256-258                               577   "          "      "          " "  256-258                               578   2-CH.sub.3, 3-OCH.sub.3                                                                  "      "          " "  217-219                               579   2-CH.sub.3, 5-OCH.sub.3                                                                  "      "          " "  218-221                               580   4-Br, 3,5-(OCH.sub.3).sub.2                                                              H      "          " "  >300                                  __________________________________________________________________________

                                      TABLE lc                                    __________________________________________________________________________    Compound                         Melting                                      No.   Xl       Ym      Zn A R    point(°C.)                            __________________________________________________________________________    581   H        2-F,4-OCH.sub.3                                                                       H  O CH.sub.3                                                                           210-212                                      582   "        2-CH.sub.3,4-OCH.sub.3                                                                "  " "    180-182                                      583   "        2-Cl    2-F                                                                              " "    177-179                                      584   "        4-F     "  " "    229-232                                      585   "        2-Cl,4-OCH.sub.3                                                                      "  " "    206-209                                      586   2-Cl,4-OCH.sub.3                                                                       H       H  " "    213-215                                      587   2-F,5-OCH.sub.3                                                                        "       "  " "    191-193                                      588   2-Br,3,5-(OCH.sub.3).sub.2                                                             "       "  " "    264-265                                      589   2,3,4-F.sub.3                                                                          "       "  " "    209-210                                      590   2-Cl,3,5-(OCH.sub.3).sub.2                                                             "       "  " C.sub.2 H.sub.5                                                                    168-170                                      591   2-F,5-OCH.sub.3                                                                        "       2-F                                                                              " CH.sub.3                                                                           173-176                                                                       206-210                                      592   2-Br,3,5-(OCH.sub.3).sub. 2                                                            "       "  " "                                                                                  234-237                                      593   2-Cl,5-OCH.sub.3                                                                       "       2-Cl                                                                             " "    186-188                                      594   2-Cl,3-OCH.sub.3                                                                       2-Cl    H  " "    270.5-271.5                                  595   "        "       "  " "    238-240                                      596   2-Br,3,5-(OCH.sub.3).sub.2                                                             "       "  " "    243.5-245.5                                  597   "        "       "  " "    227-230                                      598   3-O--C.sub.3 H.sub.7 -i                                                                "       "  " "    162-164                                      599   2-F,5-OCH.sub.3                                                                        "       "  " "    185-188                                      600   "        "       "  " "    169-174                                      601   2-Cl,5-OCH.sub.3                                                                       2-Br    "  " "    185-194                                      602   2-Cl,3-OCH.sub.3                                                                       4-Cl    H  O CH.sub.3                                                                           212-215                                      603   2-Cl,5-OCH.sub.3                                                                       "       "  " "    243-245                                      604   2-Cl,3,5-(OCH.sub.3).sub.2                                                             "       "  " "    245-247                                                                       240-243                                      605   "        2-F     "  " "                                                                                  247-250                                      606   "        "       "  " "    242-243                                                                       242-246                                      607   "        4-F     "  " "                                                                                  250-253                                      608   2-F      4-OC.sub.2 H.sub.5                                                                    "  " "    186-188                                      609   3-OCH.sub.3                                                                            "       "  " "    180-184                                      610   2-Cl     "       "  " "    168-170                                      611   3,5-(OCH.sub.3).sub.2                                                                  "       "  " "    168-171                                      612   2-Cl,5-OCH.sub.3                                                                       "       "  " "    179-182                                      613   2-Br,3,5-(OCH.sub.3).sub.2                                                             4-OCH.sub.3                                                                           "  " "    248-250                                      614   2-F      4-OCH.sub.2 C.tbd.CH                                                                  "  " "    158-161                                      615   3-OCH.sub.3                                                                            "       "  " "    173-175                                      616   3,5-(OCH.sub.3).sub.2                                                                  "       "  " "    170-171                                      617   2-Cl,3,5-(OCH.sub.3 ).sub.2                                                            2,4-F.sub.2                                                                           "  " "    226-230                                      618   "        "       "  " "    216-218                                      619   "        2-Cl,4-OCH.sub.3                                                                      "  " "    240-243                                      620   "        "       "  " "    233-235                                      621   2-CH.sub.3,3-OCH.sub.3                                                                 "       "  " "    266-269                                      622   "        "       "  " "    205-207                                      623   3,5-(OCH.sub.3).sub.2                                                                  2-CH.sub.3,4-OCH.sub.3                                                                "  " "    215-217                                      624   "        2-F,4-OCH.sub.3                                                                       "  " "    162-163                                      625   2-Cl,3,5-(OCH.sub.3).sub.2                                                             4-OCH.sub.3                                                                           2-F                                                                              " "    232-235                                      626   2-Cl,5-OCH.sub.3                                                                       4-OCH.sub.3                                                                           2-F                                                                              O CH.sub.3                                                                           243-247                                      627   2-Cl,3,5-(OCH.sub.3).sub.2                                                             2-Cl    "  " "    256-257                                                                       213-215                                      628   "        "       "  " "                                                                                  235-236                                      629   2-Cl,5-OCH.sub.3                                                                       "       "  " "    200-201                                      630   "        "       "  " "    207-208                                      631   2-Br,3,5-(OCH.sub.3).sub.2                                                             "       "  " "    237-239                                      632   "        "       "  " "    245-247                                      633   3,5-(OCH.sub.3).sub.2                                                                  "       "  " "    184-185                                      634   2-Cl,3,5-(OCH.sub.3).sub.2                                                             2-F     "  " "    252-254                                      635   "        "       "  " "    251-253                                      636   2-Cl,5-OCH.sub.3                                                                       "       "  " "    200-201                                      637   "        "       "  " "    184-186                                      638   "        4-F     "  " "    194-198                                      639   3,5-(OCH.sub.3).sub.2                                                                  "       "  " "    195-200                                      640   2-Cl,5-OCH.sub.3                                                                       2,4-F.sub.2                                                                           "  " "    183-185                                      641   "        "       "  " "    169-174                                      642   3,5-(OCH.sub.3).sub.2                                                                  "       "  " "    170-171                                      643   2-Cl,5-OCH.sub.3                                                                       2-Cl,4-OCH.sub.3                                                                      "  " "    252-256                                      644   "        "       "  " "    210-212                                      645   3,5-(0CH.sub.3).sub.2                                                                  "       "  " "    210-214                                      646   2-Cl,3,5-(OCH.sub.3).sub.2                                                             2,4-F.sub.2                                                                           "  " "    238-240                                      647   "        "       "  " "    229-232                                      __________________________________________________________________________

                                      TABLE 1d                                    __________________________________________________________________________    Compound                                     Melting                          No.   Xl        Ym       Zn      A R         point (°C.)               __________________________________________________________________________    648   H         2-Cl     H       O C.sub.2 H.sub.5                                                                         191-194                          649   "         4-OCHF.sub.2                                                                           "       " CH.sub.3  165-166                          650   2-Cl, 5-OCH.sub.3                                                                       2,4-F.sub.2                                                                            "       " "         184-186                          651   2-Cl, 3,5-(OCH.sub.3).sub.2                                                             4-OCH.sub.3                                                                            "       " "         230-232                          652   3,5-(OCH.sub.3).sub.2                                                                   H        2-CH.sub.2 OC.sub.2 H.sub.5                                                           " "         159-160                          653   2-Cl      3-CH.sub.3                                                                             "       " "         247-251                          654   2-F       "        "       " "         228-231                          655   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         210-211                          656   H         H        4-CH.sub.2 OCH.sub.3                                                                  " "         145-146                          657                                                                                  ##STR31##                                                                              "        H       " "         >300                             658   2-F       4-OCH.sub.2 CCH                                                                        "       " "         158-161                          659   3,5-(OCH.sub.3).sub.2                                                                   2-F, 4-OCH.sub.3                                                                       2-F     " "         103-105                          660   H         2-F      "       " "         180-183                          661   3-C.sub.3 H.sub.7 i                                                                     H        H       " "         189-191                          662                                                                                  ##STR32##                                                                              "        "       " "         177-179                          663   3,5-(OCH.sub.3).sub.2                                                                   2,3-F.sub.2                                                                            "       " "         227-229                          664   "         3,5-(CH.sub.3).sub.2                                                                   "       " "         242-244                          665   "         2-F      2-F     S "         226-228                          666   "         4-OC.sub.3 H.sub.7                                                                     H       O "         149-150                          667   2-Cl, 5-OCH.sub.3                                                                       "        "       " "         189-190                          668   "         H        3-F     " "         236-239                          669   "         "        H       " Cl        255-256                          670   "         "        2-F     S CH.sub.3  243-245                          671                                                                                  ##STR33##                                                                              "        H       O "                                                                                        ##STR34##                       672                                                                                  ##STR35##                                                                              "        "       " "         233-237                          673   2-Cl, 5-OCH.sub.3                                                                       H        H       S CH.sub.3  251-253                          674   H                                                                                        ##STR36##                                                                             "       O "         253-254                          675   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         195-196                          676   2-Cl,3,5-(OCH.sub.3).sub.2                                                              "        "       " "         208-209                          677   "         H        2-F     S "         209-211                          678   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         241-243                          679   "         2,4-F.sub.2                                                                            "       " "         216-217                          680   "         H        H       " "         259-261                          681   2-Cl,5-OCH.sub.3                                                                        4-OCH.sub.2 CCH                                                                        "       O "         192-193                          682   H         4-OC.sub.4 H.sub.9                                                                     "       O "         150-151                          683   2-Cl, 5-OCH.sub.3                                                                       "        "       " "         179-183                          684   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         118-119                          685   2-CH.sub.3, 3-OCH.sub.3                                                                 2,4-F.sub.2                                                                            "       " "         208- 209                         686   H         2,4-F.sub.2                                                                            2-F     " "         213-214                          687   "         2-F      2-Cl    " "         196-200                          688   2-F, 4-Cl H        H       " "         216-218                          689   2-Cl, 4-F "        "       " "         268-269                          690   3,5-(OCH.sub.3).sub.2                                                                   "        2,3-F.sub.2                                                                           " "         218-219                          691   H         "        H       " CCH       250-253                          692   "         "        "       " CCSi      202-203                                                             (CH.sub.3).sub.3                           693   3,5-(OCH.sub.3).sub.2                                                                   2-F      2-F     " Cl        236-238                          694                                                                                  ##STR37##                                                                              H        H       " CH.sub.3  157-159                          695   2-NO.sub.2, 3,5-(OCH.sub.3).sub.2                                                       "        "       " "                                                                                        ##STR38##                       696   2-Cl, 5-OCH.sub.3                                                                       2-Cl     "       S "         269-271                          697   2-Cl, 5-OCH.sub.3                                                                       2-Cl     H       S CH.sub.3  251-253                          698   2-Cl, 3,5-(OCH.sub. 3).sub.2                                                            H        "       " "         255-258                          699                                                                                  ##STR39##                                                                              "        "       O "         >300                             700   H         2,4-F.sub.2                                                                            2-Cl    " "         193-194                          701   "         H        2-F, 3-Cl                                                                             " "         199-200                          702   "         2-F      2,4-F.sub.2                                                                           " "         182-183                          703                                                                                  ##STR40##                                                                              H        H       " "         283-284                          704                                                                                  ##STR41##                                                                              "        "       " "                                                                                        ##STR42##                       705                                                                                  ##STR43##                                                                              "        "       " "         188-189                          706                                                                                  ##STR44##                                                                              "        "       " "         >300                             707   3-NHCH.sub.3                                                                            "        "       " "         282-283                          708   4-NHCH.sub.3                                                                            "        "       " "         248-249                          709   H                                                                                        ##STR45##                                                                             "       " "         262- 265                         710   3,5-(OCH.sub.3).sub.2                                                                    ##STR46##                                                                             "       " "         211-212                          711   H         H                                                                                       ##STR47##                                                                            " "         209-210                          712   "         2-Cl     2-F     S "         196-199                          713   3,5-(OCH.sub.3).sub.2                                                                   4-OCH.sub.3                                                                            H       " "         227-232                          714   "         2-Cl     "       " "         245-249                          715   H                                                                                        ##STR48##                                                                             "       O "         >300                             716   H         2-F, 3-Cl                                                                              H       O CH.sub.3  216-217                          717   "         3,5-F.sub.2                                                                            "       " "         205-206                          718   "         2-F      2-F     " Cl        219.5-220                        719   3,5-F.sub.2                                                                             H        H       " CH.sub.3  268-269                          720   2-OCH.sub.2 CCH                                                                         "        "       " "         165-167                          721   2-Cl, 5-NH.sub.2                                                                        "        "       " "         >300                             722                                                                                  ##STR49##                                                                              "        "       " "         >300                             723                                                                                  ##STR50##                                                                              "        "       " "         239-240                          724   2-Cl, 5-NHCH.sub.3                                                                      "        "       " "         235-237                          725                                                                                  ##STR51##                                                                              "        "       " "         203-205                          726   H         "                                                                                       ##STR52##                                                                            " "         181-183                          727   2-Cl, 5-OCH.sub.3                                                                       "        "       " "         183-185                          728   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         228-229                          729   H         2,3-(CH.sub.3).sub.2                                                                   H       " "         250-254                          730   2-Cl      H        2-CH.sub.3                                                                            " "         194-197                          731   2-Cl, 5-OCH.sub.3                                                                       "        "       " "         194-197                          732   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         215-217                          733   3-OCH.sub.3                                                                             2-F      H       " "         161-163                          734   "         "        2-F     " "         194-195                          735   3,5-(OCH.sub.3).sub. 2                                                                  "        2,4-F.sub.2                                                                           " "         210-212                          736   H         4-CH.sub.2 OCH.sub.3                                                                   H       " "         174-175                          737   "         4-I      "       " "         253-255                          738   3-OCH.sub.3                                                                             2-F      2,4-F.sub.2                                                                           O CH.sub.3  169-171                          739   "         2-Cl     2-F     " "         173-174                          740   2-Cl      H        4-CH.sub.2 OCH.sub.3                                                                  " "         177-179                          741   2-Cl, 5-OCH.sub.3                                                                       "        "       " "         184-185                          742   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         160-162.5                        743   H         2-Cl     2-F     " "         223-224                          744                                                                                  ##STR53##                                                                              H        H       " "         219-221                          745   2-Cl      "                                                                                       ##STR54##                                                                            " "         237-240                          746   H         "        3-F, 4-OCH.sub.3                                                                      " "         180-181                          747   "         2,6-F.sub.2, 4-Br                                                                      H       " "         189-190                          748   H         2-Cl     2,4-F.sub.2                                                                           " "         165-168                          749   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         205-206                          750   H         H        3,5-F.sub.2                                                                           " "         234-236                          751   "         "        2,6-F.sub.2, 4-Br                                                                     " "         210-215                          752   2, Cl, 4-NO.sub.2                                                                       4-F      H       " "         114-120                          753                                                                                  ##STR55##                                                                              H        "       " "         197-199                          754                                                                                  ##STR56##                                                                              "        "       " "         193-195                          755   2-Cl, 5-OCH.sub.3                                                                        ##STR57##                                                                             "       " "         244-246                          756   4-OCH.sub.2 CCH                                                                         H        "       " "         263-265                          757   4-OC.sub.3 H.sub.7                                                                      "        "       " "         189-190                          758                                                                                  ##STR58##                                                                              "        "       " "         265-268                          759   H         "        3,4-F.sub.2                                                                           " "         188-189                          760   H         2-F      2,3-F.sub.2                                                                           O CH.sub.3  151-153                          761   "         2-Cl     "       " "         206-207                          762   2-F, 5-NH.sub.2                                                                         H        H       " "         290-292                          763   2-CH.sub.3, 3-NO.sub.2                                                                  "        "       " "         241-242                                5-OCH.sub.3                                                             764   H                                                                                        ##STR59##                                                                             "       " "         162-164                          765   2-Cl      "        "       " "         156-160                          766   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         164-165                          767   H         H        2-Cl,   " "         235-236                                                   3,5-(OCH.sub.3).sub.2                                768   2-Cl      "        "       " "                                                                                        ##STR60##                       769   2-Cl, 5-OCH.sub.3                                                                       "        "       " "                                                                                        ##STR61##                       770   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         222-223                          771                                                                           772   H         2-NO.sub.2                                                                             H       " "         242-243                          773   "         3-NO.sub.2                                                                             "       " "         244- 246                         774   "         4-NO.sub.2                                                                             "       " "         206-207                          775   "         H        2-NO.sub.2                                                                            " "         161-164                          776   2-Cl      "        "       " "                                                                                        ##STR62##                       777   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "         256-258                          778   H         2-Cl     "       " "                                          779   "         2-F      "       " "                                          780   2-Cl      2-NO.sub.2                                                                             H       " "                                          781   3,5-(OCH.sub.3).sub.2                                                                   2-NO.sub.2                                                                             H       O CH.sub.3                                   782   2-Cl      3-NO.sub.2                                                                             "       " "                                          783   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "                                          784   2-Cl      4-NO.sub.2                                                                             "       " "                                          785   3,5-(OCH.sub.3).sub.2                                                                   "        "       " "                                          786   H         2-NO.sub.2                                                                             2-Cl    " "                                          787   "         "        2-F     " "                                          788   3-OCH.sub.3                                                                             2-Cl     2,4-F.sub.2                                                                           " "         159-160                          789   3-OCH.sub.3                                                                             2,4-F.sub.2                                                                            H       " "         168-169                          790   "         "        2-F     " "         136.5-138                        791   "         "        2,4-F.sub.2                                                                           " "         137-138                          792   2,5-Cl.sub.2                                                                            H        H       " "         245-255                                3-CF.sub.3                                                              793   3,5-(OCH.sub.3).sub.2                                                                   2-F      2-F     " CH.sub.2 OC.sub.2 H.sub.5                                                               189-191                          794   3,5-(OCH.sub.3).sub.2                                                                   "        "       "                                                                                ##STR63##                                                                              88-91                            795   "         "        "       " CH.sub.2 OH                                                                             162-164                          796                                                                                  ##STR64##                                                                              H        H       " CH.sub.3  252-253                          797   H         H        H       " CH.sub.2 F                                                                              180-181                          __________________________________________________________________________

In Table 1a-Table 1d, when "H" is given in the columns of "X_(l) ","Y_(m) " and/or "Z_(n) ", this means that the value of l, m and/or n isor are zero, respectively.

In Table 1a, Compound 2 is a salt with 1/3 HCl, Compound 308 a salt with1/2 HCl, and Compound 446 a salt with ##STR65##

Further, pairs of Compound 335 and Compound 336; Compound 338 andCompound 339; Compound 365 and Compound 364; Compound 366 and Compound367; Compound 368 and Compound 369; Compound 415 and Compound 416;Compound 426 and Compound 427; Compound 428 and Compound 429; Compound431 and Compound 432; Compound 451 and Compound 452; Compound 453 andCompound 454; and Compound 515 and Compound 516 are respectively in therelationship of atrop-isomers. Compound 337 is a mixture of isomers.

In Table 1b, pairs of Compound 560 and Compound 561; Compound 564 andCompound 565; Compound 566 and Compound 567; Compound 574 and Compound575; and Compound 576 and Compound 577 are respectively in therelationship of atrop-isomers. Compound 580 showed the followingspectrum peaks:-

IR spectrum (KBr, cm⁻¹): 1620, 1230, 1020,

NMR spectrum (CDCl₃, 8 ppm): 6.00 (2H, s), 6.58(1H, s), 7.00-7.40(10H,m).

In Table 1c, Compound 610 is a hydrate with 1/2 H₂ O.

Further, pairs of Compound 594 and Compound 595; Compound 596 andCompound 597; Compound 599 and Compound 600; Compound 605 and Compound606; Compound 617 and Compound 618; Compound 619 and Compound 620;Compound 621 and Compound 622; Compound 627 and Compound 628; Compound629 and Compound 630; Compound 631 and Compound 632; Compound 634 andCompound 635; Compound 636 and Compound 637; Compound 640 and Compound641; Compound 643 and Compound 644; and Compound 646 and Compound 647are respectively in the relationship of atrop-isomers.

In Table 1d, a pair of Compound 696 and compound 697 is in therelationship of atrop-isomers. Further, Compound 695Compound 704 andCompound 776 include different crystalline forms, respectively.

Amongst the compounds of formula (I) according to this invention, thecompounds of the formulae listed below are most preferred: ##STR66##

Next, some examples of the compounds of formula (I) of this inventionwere examined by certain analytical instruments to investigate theircharacteristic absorptions of the infrared absorption spectrum (IRspectrum) and nuclear magnetic resonance absorption spectrum (NMRspectrum). The results obtained are summarized in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Compound                                                                              Analytical                                                            No.     method         Characteristics                                        ______________________________________                                                IR-spectrum    2900- 2300, 1615                                               (KBr, cm.sup.-1)                                                      28                                                                                    NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       IR-spectrum    2800- 2300, 1610                                               (KBr, cm.sup.-1)                                                      29                                                                                    NMR-spectrum   1.73(3H,s), 6.30-6.85(6H,m),                                   (DMSO--d.sub.6, δ ppm)                                                                 7.67(10H,s)                                                    IR-spectrum    1615, 1275, 1240                                               (KBr, cm.sup.-1)                                                      30      NMR-spectrum   Not measurable due to                                                         insolubility in volvents                                       Mass-spectrum  353 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    1620                                                           (KBr, cm.sup.-1)                                                              NMR-spectrum   1.63(3H,s), 5.20(2H.bs)                                38      (DMSO--d.sub.6, δ ppm)                                                                 5.90-6.90(5H,m),                                                              7.00-7.63(10H,m)                                               Mass-spectrum  352 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    3420, 3300, 1620, 1275                                         (KBr, cm.sup.-1)                                                      40                                                                                    NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       IR-spectrum    1610, 1050                                                     (KBr, cm.sup.-1)                                                      47                                                                                    NMR-spectrum   1.93(3H,s), 2.27(3H,s),                                        (CDCl.sub.3, δ ppm)                                                                    6.57(1H,s), 6.90-7.30(14H,m)                                   IR-spectrum    3200, 1620                                                     (KBr, cm.sup.-1)                                                      64                                                                                    NMR-spectrum   1.87(3H,s), 2.98(1H,s),                                        (CDCl.sub.3, δ ppm)                                                                    6.49(1H,s), 6.60-7.20(14H,m)                                   IR-spectrum    1625                                                           (KBr, cm.sup.-1)                                                      112     NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       Mass-spectrum  385 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    1625, 1520, 1350, 850                                          (KBr, cm.sup.-1)                                                      140     NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       Mass-spectrum  396 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    3150, 1605, 1600-1440,                                         (KBr, cm.sup.-1)                                                                             1160, 765, 700                                         141                                                                                   NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       IR-spectrum    1620                                                           (KBr, cm.sup.-1)                                                      163                                                                                   NMR-spectrum   6.70(1H,s), 6.80-7.47                                          (CDCl.sub.3, δ ppm)                                                                    (14H,m)                                                        IR-spectrum    3500-3200, 1620                                                (KBr, cm.sup.-1)                                                      204                                                                                   NMR-spectrum   1.77(3H,s), 6.23(1H,s),                                        (CDCl.sub.3 /DMSO-d.sub. 6,                                                                  6.50-7.40(14H,m)                                               δ ppm)                                                                  IR-spectrum    3050, 1600, 1585-1480,                                         (KBr, cm.sup.-1)                                                                             1290, 770, 700                                         205                                                                                   NMR-spectrum   1.90(3H,s), 6.50-7.50(16H,m)                                   (CDCl.sub.3 /DMSO-d.sub. 6,                                                   δ ppm)                                                                  IR-spectrum    3400, 1605                                                     (KBr, cm.sup.-1)                                                      206                                                                                   NMR-spectrum   1.76(3H,s), 6.24(1H,s),                                        (DMSO-d.sub.  6,                                                                             6.40-7.50(14H,m)                                               δ ppm)                                                                  IR-spectrum    3120, 2980, 1720, 1615,                                        (KBr, cm.sup.-1)                                                                             1270, 750                                              272                                                                                   NMR-spectrum   1.33(3H,t), 2.00(3H,s), 4.33                                   (CDCl.sub.3, δ ppm)                                                                    (2H,q), 7.00-7.95(15H,m)                                       IR-spectrum    3050, 1600, 1590-1440,                                         (KBr, cm.sup.-1)                                                                             1280, 750, 690                                         274                                                                                   NMR-spectrum   1.80(3H,s), 6.30-7.30(16H,m)                                   (CDCl.sub.3, δ ppm)                                                     IR-spectrum    3800-2200, 1620, 1295, 760                                     (KBr, cm.sup.-1)                                                      275                                                                                   NMR-spectrum   1.66(3H,s), 6.30(1H,s),                                        (DMSO-d.sub. 6,                                                                              6.50-7.40(15H,m)                                               δ ppm)                                                                  IR-spectrum    3050, 3000-2200, 1700,                                         (KBr, cm.sup.-1)                                                                             1610, 770                                              295                                                                                   NMR-spectrum   1.90(3H,s), 6.90-7.90(16H,m)                                   (DMSO-d.sub. 6,                                                               δ ppm)                                                                  IR-spectrum    3400, 3200-1800, 1705,                                         (KBr, cm.sup.-1)                                                                             1610, 1230                                             296                                                                                   NMR-spectrum   1.75(3H,s), 6.33(1H,s),                                        (CDCl.sub.3 /DMSO-d.sub. 6,                                                                  7.00-8.20(15H,m)                                               δ ppm)                                                                  IR-spectrum    1620, 1305, 1150                                               (KBr, cm.sup.-1)                                                      299                                                                                   NMR-spectrum   1.90(3H,s), 3.10(3H,s),                                        (CDCl.sub.3, δ ppm)                                                                    6.80-8.00(14H,m), 8.40(1H,s)                                   IR-spectrum    1615                                                           (KBr, cm.sup.-1)                                                      306                                                                                   NMR-spectrum   1.89(3H,s), 6.42(1H,s),                                        (CDCl.sub.3 , δ ppm)                                                                   6.67-7.33(13H,m)                                               IR-spectrumrm  1627                                                           (KBr, cm.sup.-1)                                                      326                                                                                   NMR-spectrum   1.87(3H,s), 6.45(1H,s),                                        (CDCl.sub.3, δ ppm)                                                                    6.65-7.33(13H,m)                                               IR-spectrum    3450, 1610                                                     (KBr, cm.sup.-1)                                                      331                                                                                   NMR-spectrum   1.76(3H,s), 6.25(1H,s),                                        (DMSO-d.sub. 6,                                                                              6.40-7.50(13H,m)                                               δ ppm)                                                                  IR-spectrum    3300, 1600                                                     (KBr, cm.sup.-1)                                                      332                                                                                   NMR-spectrum   1.76(3H,s), 6.00(1H, bs),                                      (CD.sub.3 OD/DMSO-d.sub. 6                                                                   6.25(1H,s), 6.80-7.20(10H,m)                                   δ ppm)                                                                  IR-spectrum    1620, 1550, 1350                                               (KBr, cm.sup.-1)                                                      379                                                                                   NMR-spectrum   1.80(3H,s), 6.50(1H,s)                                         (CDCl.sub.3, δ ppm)                                                                    6.80-7.80(13H,m)                                               IR-spectrumn   3050, 1605, 1580-1430,                                         (KBr, cm.sup.-1)                                                                             1150, 760, 700                                         391                                                                                   NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       IR-spectrum    1625, 1530, 1350, 855                                          (KBr, cm.sup.-1)                                                      414     NMR-spectrum   Not measurable due to                                                         insolubility in solvents                                       Mass-spectrum  416 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    1620                                                           (KBr, cm.sup.-1)                                                      530     NMR-spectrum   4.03(2H,s), 6.30(1H,s),                                        (CDCl.sub.3, δ ppm)                                                                    6.60-7.90(15H,m)                                               Mass-spectrum  415 (M.sup.+)                                                  (m/z)                                                                         IR-spectrum    2230, 1630                                                     (KBr, cm.sup.-1)                                                      534                                                                                   Mass-spectrum  348 (M.sup.+), 320                                             (m/z)                                                                 ______________________________________                                    

Descriptions will next be made of the production of the compounds offormula (I) according to this invention.

PROCESS (a)

The compounds of this invention may each be produced by reacting a1,5-diphenylpentanetrions derivative represented by the general formula(II): ##STR67## wherein Y, Z, R, m and n have the same meanings asdefined above, or a tautomer thereof, with an aniline derivativerepresented by the general formula (III): ##STR68## wherein X and l havethe same meanings as defined above.

The tautomers of the above compound (II) are represented by thefollowing formulae: ##STR69##

The trione derivative of the formula (II) above can usually be preparedby condensing a 1-benzoyl-1-methylacetone derivative with a benzoicester derivative in a suitable solvent, for example, tetrahydrofuran,diethyl ether or dimethoxyethane in the presence of a base such assodium hydride or sodium methylate added thereto.

For example, 1,5-diphenyl-2-methylpentane-1,3,5-trione can be preparedfrom 1-benzoyl-1-methylacetone and methyl benzoate. It is also possibleto prepare 1-(2-chlorophenyl)-2-methyl-5-phenylpentane-1,3,5-trione from1-(2-chlorobenzoyl)-1-methylacetone and methyl benzoate;5-(2-chlorophenyl)-1-(4-methoxyphenyl)-3-methylpentane-1,3,5-trione from1-(4-methoxybenzoyl)-1-methylacetone and methyl 2-chlorobenzoate; and2-benzyl-1,5-diphenylpentane-1,3,5-trione from 1-benzoyl-1-benzylacetoneand methyl benzoate.

In the Process (a), the reaction between the pentanetrione of theformula (II) or its tautomer and the aniline derivative of the formula(III) may be conducted generally by dissolving or suspending both thereactants in a suitable solvent, for example, a hydrocarbon such asbenzene, toluene or xylene, a halogenated hydrocarbon such aschlorobenzene, methylene chloride or chloroform, an ether such asdiisopropyl ether, tetrahydrofuran or dioxane, a ketone such as acetone,methyl ethyl ketone or cyclohexanone, an ester such as ethyl acetate, anitrile such as acetonitrile, an amide such as N,N-dimethylformamide,N,N-dimethylacetamide or N-methylpyrrolidone, dimethylsulfoxide, aceticacid, or the like. As an alternative, the reaction may also be conductedwithout any solvent. It is however preferable to carry out the reactionby dissolving the reactants in xylene or chlorobenzene. Here, thereaction may be allowed to proceed with or without addition of one ormore suitable reaction aids. As usable reaction aids, may be mentionedsuitable acids, for example, mineral acids such as sulfuric acid andhydrochloric acid, organic acids such as p-toluene-sulfonic acid andtriflouromethanesulfonic acid, and Lewis acids such as borontriflouride, aluminum chloride and titanium tetrachloride. In addition,the reaction may also be allowed to proceed while collecting theresultant water in a Dean-Stark trap.

Depending on the kinds of an acid and a solvent to be employed, thereaction may also be conducted in the presence of a dehydrating agentsuch as molecular sieve. When p-toluenesulfonic acid is used indimethylsulfoxide, for instance, Molecular Sieves 5-A may be used. Themolecular sieve can be used generally in an amount of 2-200 g,preferably, 50-200 g per 0.1 mole of the 1,5-diphenylpentanetrionederivative (II). The reaction may be carried out at a desiredtemperature between the solidifying point of the solvent and its boilingpoint, preferably, at a temperature in a range of from 10° C. to theboiling point of the solvent.

After completion of the reaction, the acid or molecular sieve is removedrespectively by washing it with water and an alkali solution or byfiltration or the like. Upon removal of the solvent by distillationsubsequent to extraction of the reaction product with chloroform, thecompound of this invention can be obtained. The compound of thisinvention may be purified by recrystallizing same from acetone,methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate,chloroform, hexane or the like, or subjecting same to chromatography ona silica gel column if necessary.

PROCESS (b)

The compounds of this invention may also be produced by cyclizing a5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivative represented by thegeneral formula (IV) or (V): ##STR70## wherein X, Y, Z, R, l, m and nhave the same meanings as defined above, or ##STR71## wherein X, Y, Z,R, l, m and n have the same meanings as defined above, or a tautomerthereof in the presence of an acid catalyst.

The tautomers of the above compound (IV) are represented by the genealformulae: ##STR72##

The cyclizing or ring-closing reaction of the5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivative of the formula(IV) or (V) or its tautomer may be conducted generally by dissolving orsuspending the derivative (IV) or (V) or its tautomer in a suitablesolvent, for example, a hydrocarbon such as benzene toluene or xylene, ahalogenated hydrocarbon such as chlorobenzene, methylene chloride orchloroform, an ether such as diisopropyl ether, tetrahydrofuran ordioxane, a ketone such as acetone or methyl ethyl ketone, a nitrile suchas acetonitrile, an amide such as N,N-dimethylformamide orN,N-dimethylacetamide, dimethylsulfoxide, acetic acid, or the like. Asan alternative, the cyclization reaction may also be conducted withoutany solvent. As illustrative examples of the acid catalyst, may bementioned polyphosphoric acid, sulfuric acid, p-toluenesulfonic acid,aluminum chloride, etc. The reaction may be carried out at a desiredtemperature between the solidifying point of the solvent and its boilingpoint, preferably, at a temperature in a range of from 10° C. to theboiling point of the solvent.

After completion of the reaction, ice water is added to the reactionmixture, followed by extraction with chloroform. After washing thesolution in chloroform with water and drying same, the solvent isdistilled off to afford the compound (I) of this invention. The compoundof this invention may be purified by its recrystallization from acetone,methanol, ethanol, benzene, toluene, diisopropyl ether, ethyl acetate,chloroform, hexane or the like or its chromatography on a silica gelcolumn if necessary.

PROCESS (c)

The compound of this invention can also be produced by reacting aphenylpropiolic ester derivative represented by the general formula(VI): ##STR73## wherein Z and n have the same meanings as defined above,with an N-phenyl-1-phenylethaneimine derivative represented by thegeneral formula (VII): ##STR74## wherein X, Y, Z, R, l and m have thesame meanings as defined above, in the presence of a Lewis acid such asaluminum chloride or titanium tetrachloride.

Upon conducting the reaction in accordance with the Process (c), thephenylpropiolic ester derivative of the formula (VI) and theN-phenyl-1-phenylethaneimine derivative of the formula (VII) aredissolved or suspended in a suitable solvent, for example, benzene,toluene, xylene, chlorobenzene, dimethylsulfoxide or the like. Thereaction may also be carried out without any solvent. It is howeverpreferable to dissolve both the reactants in toluene and then to add0.5-5 equivalents of a Lewis acid as a reaction aid. As the Lewis acid,may be used aluminum chloride, titanium tetrachloride, borontriflouride, boron trichloride or the like. It is preferable to add 1equivalent of aluminum chloride.

After completion of the reaction, the reaction mixture is washedsuccessively with an aqueous solution of hydrochloric acid, water and analkali solution. After extraction with chloroform, the resultantchloroform solution is dried and the solvent is then distilled off toobtain the compound of this invention. If necessary, the compound ofthis invention can be purified by subjecting it to chromatography on asilica gel column for its crystallization and then recrystallizing samefrom acetone, methanol, benzene, ethyl acetate, chloroform or the like.When the reaction mixture is washed only with dilute hydrochloric acidand water and is not washed with an aqueous alkali solution subsequentto the completion of the reaction, the compound of the present inventionis obtained in the form of its hydrochloric acid salt. For instance, inthe case of 2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone asobtained without washing the reaction mixture with an aqueous alkalisolution, this product showed it NMR spectrum, of which the peakcorresponding to the C-5 proton shifted to a lower magnetic field ascompared with usual pyridinone derivatives, and the elemental analysisindicated the inclusion of 1/2 HC1. From this, it was confirmed that theproduct was the hydrochloride salt.

PROCESS (d)

Using as starting compound such a 4(1H)-pyridinone derivatives whichhave been prepared in the above-described procedures, other4-(1H)-pyridinone derivatives can also be produced therefrom.

For example, when2-(4-methoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone is eitherdissolved or suspended in a suitable solvent, e.g., methylene chloride,benzene or chloroform, and a Lewis acid such as boron tribromide, borontrichloride or the like is then added to the resulting solution toconduct a reaction,2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone is produced.

Further, upon dissolution of the2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone as above ina suitable solvent, for example, dimethylsulfoxide, dimethylacetamide,dimethylformamide or acetone, followed by reaction with an alkyl halide,alkoxyalkyl halide, an alkenyl halide or the like, the correspondinglysubstituted 4(1H)-pyridinone derivative is produced.

For example, the reaction with ethyl iodine gives2-(4-ethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone, and thereaction with methoxymethyl chloride provides the2-(4-methoxymethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone.

Furthermore when1-(2-nitrophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone is reduced withhydrogen, ammonium formate or the like in the presence of a palladiumblack catalyst,1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4-(1H)-pyridinone can beprepared.

Moreover, by reacting3-methyl-1-(4methylthiophenyl)-2,6-diphenyl-4(1H)-pyridinone with asuitable oxidizing agent, for example, m-chloroperbenzoic acid or Oxonein a suitable solvent such as methylene chloride or an aqueous solutionof chloroform-methanol,1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone or1-(4-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone canbe produced correspondingly.

PROCESS (e)

The 4(1H)-pyridinone derivatives of formula (I) where A is the sulfuratom can be produced by dissolving or suspending the corresponding4(1H)-pyridinone derivative of formula (I) where A is the oxygen atom,in a suitable solvent, for example, pyridinone, xylene or toluene, andthen reacting it with phosphorus pentasulfide, silicon disulfide, boronsulfide or the like under the refluxing temperature conditions.

According to a further aspect of this invention, therefore, there isprovided a process for the production of a compound of the generalformula (I) as described hereinbefore, which process comprises the stepof:

either (i) reacting a 1,5-diphenylpentanetrione derivative representedby the general formula (II): ##STR75## wherein Y, Z, R, m and n have thesame meaning as defined above, or a tautomer thereof, with an anilinederivative represented by the general formula (III): ##STR76## wherein Xand l have the same meanings as defined above, in an inert organicsolvent, or

(ii) cyclizing a 5-anilino-1,5-diphenyl-4-pentene-1,3-dione derivativerepresented by the general formula (IV) or (V): ##STR77## wherein X, Y,Z, R, l, m and n have the same meanings as defined above, or ##STR78##wherein X, Y, Z, R, l, m and n have the same meanings as defined above,or a tautomer thereof in or without an inert organic solvent in thepresence of an acid catalyst, or

(iii) reacting a phenylpropionic ester derivative represented by thegeneral formula (VI): ##STR79## wherein X and n have the same meaningsas defined above, with an N-phenyl-1-phenylethaneimine derivativerepresented by the general formula (VII): ##STR80## wherein X, Y, R, land m have the same meaning as defined above, in or without an inertorganic solvent, in the presence of a Lewis acid such as aluminumchloride or titanium tetrachloride, or

(iv) reacting a 4(1H)-pyridinone derivative represented by the generalformula ##STR81## wherein X, Y, Z, R, m, n and l are defined above, withphosphorus pentasulfide, silicon disulfide, boron sulfide or otherequivalent sulfurizing agent in an inert organic solvent under therefluxing temperature to convert the oxygen atom at the 4-position ofthe compound of the formula (I') into a sulfur atom which is a value ofthe group A in the compound of the formula (I).

Incidentally, when at least one phenyl group among the three phenylgroups at the 1-, 2-, and 6-positions of the compounds of this inventionas produced in the above-described processes is containing at least onesubstituent at each of the ortho- or meta-positions thereof, theatrop-isomers exist. The atrop-isomers can be isolated from each otherby chromatography on a silica gel column except for enantiomers.

Production of the compounds of this invention will now be illustratedwith reference to the following Examples 1-33. Examples 1-10 and 30-32are illustrative of the Process (a), Examples 11 illustrative of theProcess (b), Examples 12-21 and 33 illustrative of the Process (c),Examples 22-26 and 28-29 illustrative of the Process (d), and Example 27is illustrative of the Process (e).

EXAMPLE 1 Synthesis of1-(3,5-dimethoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

to 170 ml of chlorobenzene were added 4.2 g (0.015 mole) of2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 11.5 g (0.075 mole) of3,5-dimethoxyaniline, 5.2 g (0.027 mole) of para-toluenesulfonic acidand 35.0 g of Molecular Sieves 5A, followed by refluxing the resultingmixture for 2 hours. After cooling the reaction mixture, solid matterwas removed from the reaction mixture, followed by addition of 200 ml ofchloroform thereto. The organic layer was washed first with 200 ml of10% hydrochloric acid and then with 200 ml of a 10% aqueous solution ofsodium hydroxide. The organic layer was washed further with water andwas then dried over anhydrous sodium sulfate. Subsequent to removal ofthe sodium sulfate by filtration, the solvent was distilled off and theresidue was subjected to chromatography on a silica gel column (eluent:ethyl acetate). Upon recrystallization of the resultant crystals from a2:1 mixed solvent of acetone and hexane, 2.0 g of1-(3,5-dimethoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 232°-236° C. was obtained.

EXAMPLE 2 Synthesis of 1-(2,6-diflourophenyl)-b3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 150 ml of xylene were added 2.8 g (0.010 mole) of2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 12.9 g (0.010 mole) of2,6-diflouroaniline, 3.0 g (0.016 mole) of para-toluenesulfonic acid and30.0 g of Molecular Sieves 5A, followed by refluxing the resultingmixture for 3 hours. After cooling the reaction mixture, solid matterwas filtered off and the filtrate was washed successively with 50 ml of10% hydrochloric acid, 50 ml of 10% aqueous solution of sodium hydroxideand water. The filtrate was then dried over anhydrous sodium sulfate.Subsequent to removal of the sodium sulfate by filtration, the solventwas distilled off and the residue was crystallized from a 2:1 mixedsolvent of acetone and hexane to give 0.7 g of1-(2,6-diflourophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 219°-221° C.

EXAMPLE 3 Synthesis of1-(2-chloro-5-nitrophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 170ml of chlorobenzene were added 3.4 g (0.012 mole) of2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 10.4 g (0.060 mole) of2-chloro-5-nitroaniline, 4.1 g (0.022 mole) of para-toluenesulfonic acidand 35.0 g of Molecular Sieves 5A, followed by refluxing for 2 hours.After cooling the reaction mixture, solid matter was removed from thereaction mixture, followed by addition of 200 ml of chloroform. Theresultant mixture was washed first with 100 ml of 10% hydrochloric acidand then with 100 ml of a 10% aqueous solution of sodium hydroxide. Themixture was washed further with water and was then dried over anhydroussodium sulfate. Subsequent to removal of the sodium sulfate, the solventwas distilled off and the residue was purified by chromatography on asilica gel column (eluent: ethyl acetate). Upon recrystallization of theresultant crystals from a 2:1 mixed solvent of acetone and hexane, 1.9 gof 1-(2-chloro-5-nitrophenyl)-3-methyl-2,6 -diphenyl-4(1H)-pyridinonehaving a melting point of 277°-279° C. was obtained.

EXAMPLE 4 Synthesis of1-2(2,4-dichloro-3-methylphenyl-3-methyl-2,6-diphenyl-4(1H)-pyridinone

In 170 ml of chlorobenzene were dissolved 3.4 g (0.012 mole) of2-methyl-1,5-diphenyl-1,3,5-pentanetrione and 10.6 g (0.06 mole) of2,4-dichloro-3-methylaniline, followed by further addition of 4.1 g(0.022 mole) of para-toluenesulfonic acid and 35.0 g of Molecular Sieves5A to the solution. After heating the reaction mixture under reflux for2 hours, solid matter was removed from the reaction mixture, followed byan addition of 200 ml of chloroform. The resultant mixture was washedfirst with 100 ml of 10% hydrochloric acid and then with 100 ml of a 10%aqueous solution of sodium hydroxide. The mixture was washed furtherwith water and was then dried over anhydrous sodium sulfate. Subsequentto removal of the sodium sulfate, the solvent was distilled off and theresidue was purified by chromatography on a silica gel column (eluent:ethyl acetate). Upon recrystallization of the resultant crystals from a2:1 mixed solvent of acetone and hexane, 0.7 g of1-(2,4-dichloro-3-methylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinonehaving a melting point of 237°-238° C. was obtained.

EXAMPLE 5 Synthesis of2-(3-ethoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

In 500 ml of xylene were dissolved 15.0 g (0.046 mole) of1-(3-ethoxyphenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 43.0 g (0.47mole) of aniline and 8.8 g (0.092 mole) of methanesulfonic acid. Thereaction mixture was heated under reflux for 30 minutes in a reactorfitted with a Dean-Stark apparatus. After cooling, the reaction mixturewas filtered to remove solid matter, followed by removal of the solventby distillation. The residue was extracted with chloroform and theresultant solution in chloroform (the extract) was washed first with 100ml of 10% hydrochloric acid and then with 100 ml of a 10% aqueoussolution of sodium hydroxide. The chloroform solution was washed furtherwith water and was then dried over anhydrous sodium sulfate. Subsequentto removal of the sodium sulfate, the solvent was distilled off and theresidue was subjected to chromatography on a silica gel column (eluent:ethyl acetate). Upon recrystallization of the resultant crystals fromacetone, 5.3 g of2-(3-ethoxyphenyl)-3-methyl-1,6-diphenyl-4-(1H)-pyridinone having amelting point of 146°-149° C. was obtained.

EXAMPLE 6 Synthesis of6-(4-cyanophenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone

In 400 ml of xylene were dissolved 10.0 g (0.033 mole) of5-(4-cyanophenyl)-2-methyl-1-phenyl-1,3,5-pentanetrione, 25.0 g (0.26mole) of aniline and 7.0 g (0.073 mole) of methanesulfonic acid. Thesolution obtained was heated under reflux for 30 minutes in a reactorfitted with a Dean-Stark apparatus. After cooling, 6.5 g (0.043 mole) oftrifluoromethanesulfonic acid was added further to the reaction mixtureand the resultant mixture was similarly heated under reflux for 30minutes. After cooling, solid matter was removed from the reactionmixture, followed by concentration under pressure. The concentrate wasextracted with dichloromethane. The organic layer was washedsuccessively with 100 ml of 10% hydrochloric acid, 100 ml of a 10%aqueous solution of sodium hydroxide and water. The organic layer wasthen dried over anhydrous sodium sulfate. Subsequent to removal of thesodium sulfate, the solvent was distilled off and the residue wassubjected to chromatography on a silica gel column (eluent: ethylacetate). The resultant crystals were washed with acetone to afford 2.4g of 6-(4-cyanophenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone having amelting point of 229°-233° C.

EXAMPLE 7 Synthesis of2-(2-chlorophenyl)-3-methyl-1-(2-methylphenyl)-phenyl-4(1H)-pyridinone

In 500 ml of xylene were dissolved 37.7 g (0.012 mole) of1-(2-chlorophenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 38.6 g (0.36mole) of 2-methylaniline, 22.8 g (0.12 mole) of para-toluenesulfonicacid and 30 g of Molecular Sieves 5A, followed by refluxing theresulting mixture for 8 hours. After cooling, solid matter was filteredoff and the organic layer was washed first with 100 ml of 10%hydrochloric acid and then with 100 ml of a 10% aqueous solution ofsodium hydroxide. After washing the organic layer further with water, itwas dried over anhydrous sodium sulfate. Subsequent to removal of thesodium sulfate, the solvent was distilled off and the residue wassubjected to chromatography on a silica gel column (eluent: ethylacetate). As result, two atrop-isomers of2-(2-chlorophenyl)-3-methyl-1-(2-methylphenyl)-6-phenyl-4(1H)-pyridinone,namely, Compound 338 and Compound 339 were obtained in yields of 1.2 gand 0.8 g, respectively. Their melting points were 227°-229° C. and222°-225° C., respectively.

EXAMPLE 8 Synthesis of1,2,6-tris(2-chlorophenyl)-3-methyl-4(1H)-pyridinone

To 200 ml of xylene were added 6.9 g (0.020 mole) of1,5-bis(2-chlorophenyl)-2-methyl-1,3,5-pentanetrione, 25.5 g (0.20 mole)of 2-chloroaniline and 20.0 g of Molecular Sieves 5A. After heating thereaction mixture under reflux for 2 hours, the reaction mixture waspoured into ice water, followed by addition of 200 ml of chloroformthereto and vigorous stirring of the resultant mixture. One hour later,the reaction mixture was filtered to remove solid matter. The organiclayer was washed first with 50 ml of 10% hydrochloric acid and then with50 ml of a 10% aqueous solution of sodium hydroxide. The mixture waswashed further with water and was then dried over anhydrous sodiumsulfate. Subsequent to removal of the sodium sulfate, the solvent wasdistilled off. The residue was purified by chromatography on a silicagel column (eluent: ethyl acetate) and then recrystallization fromacetone to give 1.4 g of1,2,6-tris(2-chlorophenyl)-3-methyl-4(1H)-pyridinone having a meltingpoint of 205°-207° C.

EXAMPLE 9 Synthesis of6-(2-chlorophenyl)-1-(2,6-difluorophenyl)-3-methyl-2-phenyl-4(1H)-pyridinone

In 200 ml of xylene were dissolved 6.3 g (0.020 mole) of5-(2-chlorophenyl)-2-methyl-1-phenyl-1,3,5-pentanetrione, 20.0 g (0.155mole) of 2,6-difluoroaniline, 4,6 g (0.024 mole) of para-toluenesulfonicacid and 50.0 g of Molecular Sieves 5A, followed by reflux for 8 hours.Solid matter was filtered off from the reaction mixture and 300 ml ofchloroform was added to the filtrate. The mixture obtained was washedfirst with 50 ml of 10% aqueous solution of sodium hydroxide. Afterwashing the chloroform layer further with water, it was dried overanhydrous sodium sulfate. Subsequent to removal of the sodium sulfate,the solvent was distilled off and the residue was subjected to columnchromatography (eluent: ethyl acetate) to afford crystals. The crystalswere recrystallized from a 2:1 mixed solvent of acetone and hexane,thereby yielding 2.0 g of6-(2-chlorophenyl)-1-(2,6-difluorophenyl)-3-methyl-2-phenyl-4(1H)-pyridinonehaving a melting point of 213°-215° C.

EXAMPLE 10 Synthesis of3-methyl-1-(2,3,4,5,6-pentafluorophenyl)-2,6-diphenyl-4(1H)-pyridinone

In 110 ml of xylene were dissolved 3.1 g (0.011 mole) of2-methyl-1,5-diphenyl-1,3,5-pentanetrione, 20.0 g (0.11 mole) of2,3,4,5,6-pentafluoroaniline, 3.1 g (0.016 mole) of paratoluenesulfonicacid and 22.0 g of Molecular Sieves 5A, followed by reflux for 1 hours.After cooling the reaction mixture, solid matter was removed byfiltration and the filtrate was then concentrated. After 200 ml ofchloroform was added, the resultant solution in chloroform was washedfirst with 50 ml of 10% hydrochloric acid and then with 50 ml of a 10%aqueous solution of sodium hydroxide. After washing the solution inchloroform further with water, it was dried over anhydrous sodiumsulfate. Subsequent to removal of the sodium sulfate, the solvent wasdistilled off and the residue was subjected to column chromatography(eluent: 50.1 mixed solvent of chloroform and methanol). The resultingcrystals were recrystallized from a 1:1 mixed solvent of acetone andhexane, thereby affording 1.3 g of3-methyl-1-(2,3,4,5,6-pentafluorophenyl)-2,6-diphenyl-4(1H)-pyridinonehaving a melting point of 192°-194° C.

EXAMPLE 11 Synthesis of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 17.8 g (0.050 mole) of5-(2-chloroanilino)-2-methyl-1,5-diphenyl-4-pentene-1,3-dione, 200 ml ofxylene and 100 g of polyphosphoric acid were added. The resultantmixture was heated under reflux for 30 minutes. After cooling thereaction mixture, the solvent was removed by decantation and theremaining solid matter was added with 200 ml of chloroform and 200 ml ofwater. The resultant mixture was then stirred vigorously for 2 hours.Thereafter, the organic layer was washed with water and then dried overanhydrous sodium sulfate. After removal of the sodium sulfate, thesolvent was distilled off and the residue was recrystallized fromacetone, thereby affording 2.8 g of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 228°-231° C.

EXAMPLE 12 Synthesis of1-(4-fluorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 9.1 g (0.040 mole) ofN-(4fluorophenyl)-1-phenylpropaneimine, 4.7 g (0.035 mole) of aluminumchloride and 5.2 g (0.030 mole) of ethyl phenylpropiolate, followed byrefluxing the resultant mixture for 5 hours. Thereafter, the reactionmixture was poured into 500 ml of 2N sulfuric acid which had beenice-cooled, followed by extraction with chloroform. After washing theorganic layer with water, the organic layer wad dried over anhydroussodium sulfate. Subsequent to removal of the sodium sulfate, the solventwas distilled off and the residue was purified by chromatography on asilica gel column (eluent: 1:50 mixed solvent of methanol andchloroform). The resultant crystals were recrystallized from 1:1 mixedsolvent of acetone and hexane to give 1.0 g of1-(4-fluorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 256°-259° C.

EXAMPLE 13 Synthesis of1-(3-methoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

Added to 300 ml of benzene were 8.0 g (0.033 mole) ofN-(3-methoxyphenyl)-1-phenylpropaneimine and 4.7 g (0.035 mole) ofaluminum chloride, followed by dropwise addition of 5.2 g (0.030 mole)of ethyl phenylpropiolate at room temperature.

After heating the reaction mixture under reflux for 30 hours under anitrogen atmosphere, the reaction mixture was poured into 500 ml of 2Nsulfuric acid which had been ice-cooled, followed by extraction withchloroform. After washing the organic layer with water, it was driedover anhydrous sodium sulfate. Subsequent to removal of the sodiumsulfate, the solvent was distilled off and the residue was purified bychromatography on a silica gel column (eluent: ethyl acetate). Thecrystals obtained were recrystallized from a 2:1 mixed solvent of ethylacetate and hexane to obtain 0.8 g of1-(3-methoxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 183°-185° C.

EXAMPLE 14 Synthesis of2-(3,4-dichlorophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

To 500 ml of toluene were added 6.2 g (0.022 mole) of1-(3,4-dichlorophenyl)-N-phenylpropaneimine and 3.9 g (0.022 mole) ofethyl phenylpropiolate, followed by addition of 3.6 g (0.023 mole) ofaluminum chloride. After heating the reaction mixture with stirring at60°-70° C. for 4 days under a nitrogen atmosphere, the reaction mixturewas poured into 400 ml of 2N sulfuric acid which had been ice-cooled,followed by extraction with dichloromethane. After washing the organiclayer with water, it was dried over anhydrous sodium sulfate. Subsequentto removal of the sodium sulfate, the solvent was distilled off and theresidue was purified by chromatography on a silica gel column (eluent:ethyl acetate). The resulting crystals were recrystallized from a 2:1mixed solvent of acetone and hexane to afford 1.9 g of2-(3,4-dichlorophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone having amelting point of 188°-191° C.

EXAMPLE 15 Synthesis of6-(2-methylphenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 7.5 g (0.036 mole) ofN-phenyl-1-phenylpropaneimine, 5.8 g (0.031 mole) of ethyl2-methylphenylpropiolate and 6.0 g (0.045 mole) of aluminum chloride.The reaction mixture was stirred with heating at 60° C. for 3 days in anitrogen atmosphere. After cooling, the reaction mixture was poured into500 ml of 2N sulfuric acid, followed by extraction with chloroform.After washing the organic layer with water, it was dried over anhydroussodium sulfate. Subsequent to removal of the sodium sulfate, the solventwas distilled off and the residue was purified by chromatography on asilica gel column (eluent: ethyl acetate). The resultant crystals werewashed with a 2:1 mixed solvent of acetone and hexane to obtain 0.4 g of6-(2-methyl-phenyl)-3-methyl-1,2-diphenyl-4(1H)-pyridinone having amelting point of 188°-191° C.

EXAMPLE 16 Synthesis of1,2-bis(2-chlorophenyl)-3-methyl-6-phenyl-4(1H)-pyridinone

To 300 ml of toluene were added 6.2 g (0.022 mole) ofN,1-bis(2-chlorophenyl)propaneimine, 3.9 g (0.022 mole) of ethylphenylpropiolate and 3.6 g (0.027 mole) of aluminum chloride. Afterheating the reaction mixture with stirring at 60° C. for 4 days, thereaction mixture was poured into 500 ml of 2N sulfuric acid, followed byextraction with dichloromethane. After washing the organic layer withwater, it was dried over anhydrous sodium sulfate. Subsequent to removalof the sodium sulfate, the solvent was distilled off and the residue wassubjected to column chromatography (eluent: ethyl acetate) to obtain twotypes of atrop-isomers of1,2-bis(2-chlorophenyl)-3-methyl-6-phenyl-4(1H)-pyridinone, namely, 0.6g of Compound 335 and 0.2 g of Compound 336, of which the melting pointswere 205°-207° C. and 232°-234° C., respectively.

EXAMPLE 17 Synthesis of 1-(2-chlorophenyl)-2-(4-methyoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone

To 300 ml of toluene were added 6.3 g (0.023 mole) ofN-(2-chlorophenyl)1-(4-methoxyphenyl)propaneimine, 4.0 g (0.023 mole) ofethyl phenylpropiolate and 3.7 g of aluminum chloride. The reactionmixture was heated with stirring at 60° C. for 4 days. After cooling,the reaction mixture was poured into 500 ml of 2N sulfuric acid,followed by extraction with dichloromethane. After washing the organiclayer with water, it was dried over anhydrous sodium sulfate. Subsequentto removal of the sodium sulfate, the solvent was distilled off and theresidue was subjected to chromatography on a silica gel column (eluent:ethyl acetate). The crystals thus-obtained were recrystallized from a2:1 mixed solvent of acetone and hexane to give 1.0 g of1-(2-chlorophenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinone.

EXAMPLE 18 Synthesis of1-(2-chlorophenyl)-3-ethyl-2,6-diphenyl-4(1H)-pyridinone

To 300 of toluene were added 10.3 g (0.040 mole) ofN-(2-chlorophenyl)-1-phenylbutaneimine, 5.2 g (0.030 mole) of ethylphenylpropiolate and 5.3 g (0.040 mole) of aluminum chloride. Afterheating the reaction mixture under reflux for 20 hours under a nitrogenatmosphere, the reaction mixture was poured into 500 ml of 2N sulfuricacid which had been ice-cooled, followed by extraction with chloroform.After washing the organic layer with 50 ml of a 10% aqueous solution ofsodium hydroxide and then with water, it was dried over anhydrous sodiumsulfate. Subsequent to removal of the sodium sulfate, the solvent wasdistilled off and the residue was purified by chromatography on a silicagel column (eluent: ethyl acetate) so that 2.0 g of1-(2-chlorophenyl)-3-ethyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of 165°-166° C. was obtained.

EXAMPLE 19 Synthesis of3-chloro-1-(2-chlorophenyl)-2,6-diphenyl-4(1H)-pyridinone

To 300 ml of toluene were added 7.4 g (0.030 mole) of2-chloro-N-(2-chlorophenyl)-1-phenylethaneimine, 5.2 g (0.030 mole) ofethyl phenylpropiolate and 6.7 g (0.050 mole) of aluminum chloride. Thereaction mixture was then heated under reflux for 20 hours undernitrogen atmosphere. After cooling, the reaction mixture was poured into500 ml of 2N sulfuric acid, followed by extraction with chloroform.After washing the organic layer with 50 ml of a 10% aqueous solution ofsodium hydroxide and then with water, it was dried with anhydrous sodiumsulfate. Subsequent to removal of the sodium sulfate, the solvent wasdistilled off and the residue was purified by chromatography on a silicagel column (eluent: ethyl acetate) to yield3-chloro-1-(2-chlorophenyl)-2,6-diphenyl-4(1H)-pyridinone having amelting point of 230°-233° C.

EXAMPLE 20 Synthesis of2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone hydrochloride

to 300 ml of toluene were added 6.4 g (0.022 mole) of1-(2-bromophenyl)-N-phenylpropaneimine, 3.9 g (0.022 mole) of ethylphenylpropiolate and 3.6 g (0.027 mole) of aluminum chloride. Thereaction mixture was then heated at 60° C. hours. After cooling, thereaction mixture was poured into 500 ml of 2N sulfuric acid, followed byextraction with methylene chloride. After washing the organic layer (theextract) with water, the organic layer was dried over anhydrous sodiumsulfate. The solvent was distilled off and the residue was subjected tochromatography on a silica gel column (eluent: ethyl acetate). Theresultant crystals were then recrystallized from a 2:1 mixed solvent ofacetone and hexane to obtain 1.3 g of2-(2-bromophenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinonehemihydrochloride having a melting point of 236°-238° C.

Elemental analysis: Calculated for C₂₄ H₁₈ BrNO·1/2HCl: C, 66.34; H,4.29; N, 3.19%. Found: C, 66.64; H, 4.52; N, 3.22%.

EXAMPLE 21 Synthesis of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone hydrochloride

Added to 700 ml of toluene were 73.1 g (0.30 mole) ofN-(2-chlorophenyl)-1-phenylpropaneimine, 34.8 g (0.20 mole) of ethylphenylpropiolate and 40.0 g (0.30 mole) of aluminum chloride. Thereaction mixture was then heated with stirring as 60° C. for 3 days.After cooling, the reaction mixture was poured into 1000 ml of 2Nsulfuric acid, followed by extraction with chloroform. After washing theorganic layer with water, the organic layer was dried over anhydrousmagnesium sulfate. The solvent was distilled off and the residue waspurified by chromatography on a silica gel column (eluent: ethylacetate). The crystals obtained were then recrystallized from a 1:2mixed solvent of chloroform and hexane to give 17.0 g of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone. 1/5HCl havinga melting point of 229°-231° C.

Elemental analysis: Calculated for C₂₄ H₁₈ C NO·1/5HCl: C, 76.03; H,4.83; N, 3.69%. Found: C, 75.56; H, 4.91; n, 3.72%.

EXAMPLE 22 Synthesis of2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone

To 300 ml of a solution of 18.7 g (0.051 mole) of2-(4-methoxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone in methylenechloride, 25.0 g (0.010 mole) of boron tribromide was added dropwise.After stirring the resultant mixture at room temperature for 15 hours,the reaction mixture was poured into water, followed by neutralizationwith sodium hydrogen carbonate. Deposited crystals were collected byfiltration and washed with aceton, thereby affording 16.9 g of2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone having amelting point of not lower than 300° C.

EXAMPLE 23 Synthesis of3-methyl-1,6-diphenyl-2-(4-propoxyphenyl)-4(1H)-pyridinone

To 50 ml of a suspension of 0.36 g (0.018 mole) of sodium hydride inDMSO, 1.7 g (0.0048 mole) of2-(4-hydroxyphenyl)-3-methyl-1,6-diphenyl-4(1H)-pyridinone was added,followed by further dropwise addition of 1.0 g (0.0058 mole) of propyliodide. The reaction mixture was then stirred at room temperature for 6hours. The reaction mixture was thereafter poured into ice water,followed by extraction with chloroform. After washing the organic layerwith water, it was dried over anhydrous magnesium sulfate. The solventwas distilled off, followed by recrystallization from a 2:1 mixedsolvent of acetone and hexane to obtain 1.6 g of3-methyl-1,6-diphenyl-2-(4-propoxyphenyl)-4(1H)-pyridinone having amelting point of 165°-168° C.

EXAMPLE 24 Synthesis of1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

To 50 ml of a suspension of 1.8 g (0.0050 mole) of3-methyl-1-(2-nitrophenyl)-2,6-diphenyl-4(1H)-pyridinone and 0.2 g of10% Pd-C in methanol, 1.5 g (0.023 mole) of ammonium formate (as areducing agent) was added. After heating the resultant mixture underreflux for 3 hours under a nitrogen gas stream, solid matter wasfiltered off from the reaction mixture and the solvent was distilledoff. The residue was then extracted with chloroform and the organiclayer (the extract) was washed with 50 ml of a 10% aqueous solution ofsodium hydroxide. After washing the organic layer with water, it wasdried with anhydrous sodium sulfate and the solvent was then distilledoff. The crystals thus-obtained were washed with acetone to give 0.9 gof 1-(2-aminophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone having amelting point of not lower than 300° C.

EXAMPLE 25 Synthesis of1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl- 4(1H)-pyridinone

Dissolved in 30 ml of methylene chloride was 1.1 g (0.0029 mole) of3-methyl-1-(4-methylthiophenyl)-2,6-diphenyl-4(1H)-pyridinone, followedby addition of 0.6 g (0.0034 mole) of m-chloroperbenzoic acid (asoxidizing agent). After stirring the reaction mixture for 15 minutes, itwas poured into water, followed by extraction with methylene chloride.The organic layer (the extract) was washed with 20 ml of a saturatedaqueous solution of sodium hydrogen carbonate and then with water. Theorganic layer was thereafter dried over anhydrous sodium sulfate. Thesolvent was distilled off and the resulting crystals were recrystallizedform a 2:1 mixed solvent of acetone and hexane, affording 1.1 g of1-(4-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinonehaving a melting point of 242°-244° C.

EXAMPLE 26 Synthesis of1-(3-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone

In 5 ml of water was dissolved 1.2 g (0.0019 mole) of Oxone. Theresulting solution was then added dropwise to 5 ml of a methanolsolution of 0.5 g (0.0013 mole) of1-(3-methanesulfinylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone.After stirring the reaction mixture for 2 hours, it was poured intowater, followed by extraction with chloroform. The organic layer waswashed with water and was thereafter dried over anhydrous sodiumsulfate. The solvent was distilled off and the residue was crystallizedform a 2:1 mixed solvent of acetone and hexane, affording 0.4 g of1-(3-methanesulfonylphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinonehaving a melting point of 246°-248° C.

EXAMPLE 27 Synthesis of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinethione

To 40 ml of pyridine were added 1.3 g (0.0035 mole) of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone and 0.9 g(0.0042 mole) of phosphorus pentasulfide, followed by refluxing theresultant mixture for 3 hours. After cooling, the reaction mixture waspoured into water and the resulting crystals were collected byfiltration. The crystals were dissolved in 100 ml of chloroform, andwashed first with 30 ml of 2N hydrochloric acid and then with 30 ml of asaturated aqueous solution of sodium hydrogencarbonate. After washingthe chloroform solution further with water, it was dried over anhydroussodium sulfate. After removal of sodium sulfate, the solvent wasdistilled off to obtain crystals. The crystals were recrystallized froma 1:1 mixture of acetone and hexane, thereby obtaining 1.1 g of1-(2-chlorophenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinethione having amelting point of 271°-275° C.

EXAMPLE 28 Synthesis of1,2,6-triphenyl-3-trifluoromethyl-4(1H)-pyridinone

To 40 ml of 1-methyl-2-pyrrolidinone were added 2.0 g (0.0050 mole) of3-bromo-1,2,6-triphenyl-4(1H)-pyridinone, 2.7 g (0.020 mole) of sodiumtrifluoroacetate and 1.9 g (0.010 mole) of cuprous iodide. The reactionmixture was then heated at 160° C. for 5 hours in a nitrogen atmosphere.After allowing the reaction mixture to cool down, it was poured intowater, followed by extraction with ethyl ether. The organic layer (theextract) was washed with 50 ml of a saturated aqueous solution of sodiumhydrogen carbonate. After washing the organic layer further with water,it was dried over anhydrous sodium sulfate. Subsequent to removal of thesodium sulfate, the solvent was distilled off, and the residue wascrystallized from a 1:3 mixed solvent of ethyl acetate and hexane toyield 0.4 g of 1,2,6-triphenyl-3-trifluoromethyl-4(1H)-pyridinone havinga melting point of 222°-225° C.

EXAMPLE 29 Synthesis of 3-methyl-2,6-diphenyl-1-(3-propargyloxyphenyl)-4(1H)-pyridinone

To 50 ml of a suspension of 0.72 g (0.03 mole) of sodium hydride inDMSO, 3.5 g (0.01 mole) of1-(3-hydroxyphenyl)-3-methyl-2,6-diphenyl-4(1H)-pyridinone was added,followed by further dropwise addition of 1.4 g (0.012 mole) of propargylbromide. The reaction mixture was thereafter poured into ice water,followed by extraction with chloroform. After washing the organic layer(the extract) with water, it was dried over anhydrous magnesium sulfate.The solvent was distilled off, followed by recrystallization from a 2:1mixed solvent of acetone and hexane to obtain 1.5 g of3-methyl-2,6-diphenyl-1-(3-propargyloxyphenyl)-4-(1H)-pyridinone havinga melting point of 166°-169° C.

EXAMPLE 30 Synthesis of1-(3,5-dimethoxyphenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinonep-toluenesulfonate

To 200 ml of chlorobenzene were added 3.1 g (0.01 mole) of1-(4-methoxyphenyl)-2-methyl-5-phenyl-1,3,5-pentanetrione, 2.3 g (1.5mole) of 3,5-dimethoxyaniline, 2.9 g (0.015 mole) ofpara-toluenesulfonic acid and 10 g of Molecular Sieves 5A, followed byrefluxing the resulting mixture for 2 hours. After cooling the reactionmixture, solid matter was removed from the reaction mixture, followed byaddition of 500 ml of chloroform thereto. The organic layer was washedfirst with 200 ml of 10% hydrochloric acid and then with water. Theorganic layer was then dried over anhydrous sodium sulfate. Subsequentto removal of the sodium sulfate by filtration, the solvent wasdistilled off and the residue was subjected to chromatography on asilica gel column (eluent: ethyl acetate). Upon washing the resultantcrystals with ethyl acetate, 3.3 g of1-(3,5-dimethoxyphenyl)-2-(4-methoxyphenyl)-3-methyl-6-phenyl-4(1H)-pyridinonep-toluenesulfonate having a melting point of 202°-204° C. was obtained.

EXAMPLE 31 Synthesis of1-(2-fluorophenyl)-3-methyl-6-(3-methylphenyl)-2-phenyl-4(1H)-pyridinone

To 30 ml of xylene were added 2.0 g (0.0068 mole) of2-methyl-5-(3-methylphenyl)-1-phenyl-1,3,5-pentanetrione, 7.6 g (0.068mole) of 2-fluoroaniline, 2.0 g (0.012 mole) of para-toluenesulfonicacid and 14.0 g of Molecular Sieves 5A, followed by refluxing theresulting mixture for 1 hour. After cooling the reaction mixture, solidmatter was filtered off and the filtrate was mixed with 100 ml ofchloroform and then washed successively with 50 ml of 10% hydrochloricacid, 50 ml of a 10% aqueous solution of sodium hyroxide and water. Thefiltrate was then dried over anhydrous sodium sulfate. Subsequent toremoval of the sodium sulfate, the solvent was distilled off and theresidue was crystallized from a 1:3 mixed solvent of chloroform andhexane to give 1.3 g of1-(2-fluorophenyl)-3-methyl-6-(3-methylphenyl)-2-phenyl-4-(1H)-pyridinonehaving a melting point of 211°-214° C.

EXAMPLE 32 Synthesis of2-(2-chlorophenyl)-6-(2-fluorophenyl)-3-methyl-1-phenyl-4(1H)-pyridinone

In 450 ml of xylene were suspended 15.3 g of1-(2-chlorophenyl)-2-methyl-5-(2-fluoro-phenyl)-1,3,5-pentanetrione, 6.4g of aniline, 6.6 g of para-toluenesulfonic acid and 85 g of MolecularSieves 5A, followed by refluxing the resultant mixture for 8 hours.Xylene was distilled off from the reaction mixture and 300 ml ofchloroform was added to the residue. The mixture obtained was filteredand the filtrate was washed first with 10% hydrochloric acid and thenwith a 10% aqueous solution of sodium hydroxide. After washing thechloroform phase further with water, the solution in chloroform wasdried over anhydrous sodium sulfate. Subsequent to removal of the sodiumsulfate, the solvent was distilled off and the residue was purified bycolumn chromatography (eluent: ethyl acetate-n-hexane, 1:3) to affordcrude crystals. The crystals were recrystallized from ethyl acetate,yielding 4.5 g of2-(2-chlorophenyl)-6(2fluorophenyl)-3-methyl-1-phenyl-4(1H)-pyridinonehaving a melting point of 182°-183° C.

EXAMPLE 33 Synthesis of2-(2,4-difluorophenyl)-6-(2-fluorophenyl)-1-(3,5-dimethoxyphenyl)-3-methyl-4(1H)-pyridinone

In 3 l of toluene were dissolved 54.9 g (0.18 mol) ofN-(3,5-dimethoxyphenyl)-1-(2,4-difluorophenyl)propanimine and 27.5 g(0.14 mole) of ethyl (2-fluorophenyl) propionate, and the resultantsolution was placed under a nitrogen atmosphere and then admixed with23.8 g (0.18 mol) of aluminum chloride, followed by refluxing theresultant mixture for 16 hours. After cooling, the reaction mixture waspoured into 2N sulfuric acid, followed by extraction with chloroform.After washing the organic layer with 5% aqueous sodium hydroxide, andwater, it was dried over anhydrous sodium sulfate. Subsequent to removalof the sodium sulfate, the solvent was distilled off and the residue wassubjected to chromatography on a silica gel column (eluent: ethylacetate-N-hexane, 1:1). The crystals thus-obtained were recrystallizedfrom ethyl acetate to afford 7.3 g of2-(2,4-difluorophenyl)-6-(2-fluorophenyl)-1-(3,5-dimethoxyphenyl)-3-methyl-4(1H)-pyridinonehaving a melting point of 171°-173° C.

The new compounds of the formula (I) according to this invention may beformulated into a fungicidal composition by mixing with a liquid orsolid carrier or vehicle which is conventionally used in the art.According to another aspect of this invention, therefore, there isprovided a fungicidal composition for agricultural and horticulturalutilities, which comprises a compound of the general formula (I) asdefined hereinbefore or a salt thereof as the active ingredient, ncombination with a carrier for the active ingredient.

Although the new compound of this invention may be applied alone, it mayusually be admixed with a carrier, optionally together with surfactant,dispersant or auxiliary agent and then formulated in a known manner, forexample, into a dust, a wettable powder, an emulsifiable concentrate,fine particles or granules.

As suitable examples of the carriers, may be mentioned solid carrierssuch as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon,vermiculite, slaked lime, siliceous sand, ammonium sulfate and urea; andliquid carriers such as isopropyl alcohol, xylene, and cyclohexanone.Illustrative examples of the surfactant and dispersant may include saltsof alcohol-sulfuric acid esters, alkylarylsulfonic acid salts,diarylmethanedisulfonic acid salts, ligninsulfonic acid salts,polyoxyethyleneglycol ethers, polyoxyethylenealkyl aryl ethers,polyoxyethylenesorbitan monoalkylates, and so on. Suitable examples ofthe adjuvants include carboxymethylcellulose, polyethylene glycol, gumarabi, etc. These preparations can be applied after diluting same to asuitable concentration of the active ingredient, or they can be applieddirectly.

The proportion of the active ingredient in the composition may beincreased or decreased as needed. When formulated into a dust orgranules, 0.1-20 wt. % of the active ingredient is preferred. For anemulsifiable concentrate or wettable powder, 5-80 wt. % of the activeingredient is preferred.

The rate of application of the fungicidally active compound of thisinvention may vary depending on the type of the active compoundemployed, the kind of the disease to be controlled, the nature ofoccurrence of the disease, the degree of damage, environmentalconditions, the preparation form to be used, etc. When the compositionof this invention is applied directly in the form of dust or granules,it is recommendable that the rate of application of the activeingredient is suitably chosen in a range of 10 to 500 g per 10 ares.When the composition of this invention in the form of an emulsifiableconcentrate or a wettable powder is diluted with water before itsapplication and then the liquid preparation obtained is applied, it ispreferred that the concentration of the active ingredient in the dilutedliquid preparation is suitably chosen in a range of 10 to 1000 ppm.Generally, however, the compound of this invention can be applied in anamount of from about 0.1 g to about 100 kg per hectare, preferably 1 gto 10 kg per hectare. When it is sprayed to leaves and stem of plants,it is usuallly diluted to a concentration of about 0.1 to 10,000 ppm,preferably 10 to 3,000 ppm.

The fungicidal composition of this invention are now illustrated withreference to the following Examples 34-37, wherein all designations of"%" are given in percent by weight.

EXAMPLE 34 (Dust)

Two percent of Compound 1, 5% of diatomaceous earth and 93% of clay wereuniformly mixed and ground into a dust.

EXAMPLE 35 cl (Wettable Powder)

Fifty percent of Compound 7, 45% of diatomaceous earth, 2% of sodiumdinaphthylmethanedisulfonate and 3% of dosium ligninsulfonate wereuniformly mixed and ground into a wettable powder.

EXAMPLE 36 cl (Emulsifiable Concentrate)

Thirty percent of Compound 126, 20% of cyclohexanone, 11% ofpolyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and35% of methylnaphthalene were evenly dissolved together to prepare anemulsifiable concentrate.

EXAMPLE 37 (Granules)

Five percent of Compound 264, 2% of the sodium salt of the ester oflauryl alcohol and sulfuric acid, 5% of sodium ligninsulfonate, 2% ofcarboxymethylcellulose and 86% of clay were mixed together and grounduniformly. The mixture was added and kneaded with 20% of water. Theresulting mixture was formed into granules of 14-32 mesh by means of anextrusion granulator and was then dried into granules.

The fungicidal compounds of this invention have excellent properties.They show broad antibacterial and antifungal spectra against pathogenicmicroorganisms of various, agricultural and horticultural diseases ofplants, such as rice sheath blight (Rhizoctonia solani), rice blast(Pyricularia oryzae), cucumber downy mildew (Pseudoperonosporacubensis), cucumber powdery mildew (Sphaerotheca fuliginea), cucumbergray mold (Botrytis cinerea) and Alternaria sooty spot of Chinesemustard (Alternaria brassicicola). In particular, the compounds of thisinvention exhibit outstanding activity to control rice sheath blight(Rhizoctonia solani). Their fungicidal activities can appear in both thepreventive treatment and curative treatment of the plant diseases andmoreover are long-lasting. In addition, the new compounds of thisinvention are of high safety, due to their low toxicity to crops,warm-blooded animals, and a variety of fish and shellfish.

Effects of the fungicidal compounds of this invention are nowillustrated by the following Tests.

TEST 1 (Test on the preventative effects for rice sheath blight,Rhizoctonia solani)

Rice seeds (variety: Kinmaze) were sown at a rate of 15 grains each inunglazed pots having a diameter of 7 cm. The seeds were allowed to growfor 4-5 weeks in a greenhouse. A wettable powder containing a testcompound and formulated in accordance with the procedure of Example 35was diluted with water to a concentration of 500 ppm of the activeingredient, and the aqueous preparation obtained was then sprayed at arate of 10 ml per pot to the rice seedling at their 5 leaf stage. Afterdried in the air, the seedlings were inoculated at the basal parts withfungi, Rhizoctonia solani which had been cultured for 7 days in a ricehulls-wheat bran culture medium, and the inoculated rice plants werethen kept in a moist room (28° C.). Five days later, the heights oflesions formed on rice leaf sheaths were measured individually. Controlvalue (%) was then evaluated in accordance with the following equation.##EQU1##

Comparative Chemicals 1 and 2, the known compounds as identifiedhereinafter, were also tested in the same manner as above, for thecomparision purpose.

Test results obtained are shown in Table 3a, Table 3b, Table 3c andTable 3d below.

                  TABLE 3a                                                        ______________________________________                                        Com-                                                                          pound Control  Compound  Control                                                                              Compound                                                                              Control                               No.   value    No.       value  No.     value                                 tested                                                                              (%)      tested    (%)    tested  (%)                                   ______________________________________                                        1     100      29        94     64      98                                    2     100      31        80     65      99                                    3     100      32        100    66      99                                    4     86       33        100    68      80                                    5     100      34        100    69      90                                    6     100      35        100    70      95                                    7     100      36        100    71      80                                    8     100      37        100    72      85                                    9     100      38        99     73      100                                   10    100      40        98     76      100                                   11    100      42        78     77      100                                   12    100      43        92     78      100                                   13    100      44        100    79      100                                   14    100      52        100    81      100                                   15    100      53        90     82      100                                   16    92       55        100    83      98                                    17    99       56        100    84      100                                   18    83       57        99     85      99                                    19    100      58        100    86      82                                    20    100      59        87     87      93                                    22    98       60        95     88      100                                   26    96       61        95     89      86                                    27    96       63        99     90      100                                   91    100      120       89     153     99                                    92    97       121       92     155     100                                   93    100      123       93     156     80                                    95    100      124       84     159     100                                   96    100      128       99     160     97                                    97    100      129       100    161     100                                   101   99       130       100    162     98                                    102   100      131       97     164     100                                   104   100      132       100    165     100                                   105   96       133       99     166     100                                   106   98       134       100    167     100                                   107   97       135       100    168     96                                    108   95       136       97     169     97                                    109   100      137       100    170     100                                   110   99       138       97     171     98                                    111   97       139       97     172     96                                    112   96       140       100    173     99                                    113   94       142       99     174     97                                    114   99       143       100    176     100                                   116   99       145       100    178     100                                   117   98       146       97     179     100                                   118   98       149       96     180     100                                   119   99       152       100    181     100                                   182   100      213       100    255     100                                   183   100      214       100    256     99                                    184   98       217       96     257     100                                   185   100      219       98     258     99                                    186   100      220       99     259     100                                   187   100      224       100    260     100                                   188   100      226       100    261     95                                    189   100      227       100    262     92                                    192   100      229       100    266     100                                   193   100      230       100    267     100                                   194   96       235       98     268     100                                   195   100      237       97     269     99                                    196   100      238       100    270     99                                    197   100      239       100    272     96                                    198   97       241       93     273     91                                    201   73       242       100    274     94                                    202   96       244       100    275     88                                    203   99       245       100    276     87                                    206   72       246       99     277     87                                    208   88       247       100    278     94                                    209   96       249       92     279     78                                    210   100      250       100    281     100                                   211   92       252       100    282     99                                    283   97       317       99     346     99                                    284   98       318       99     347     99                                    285   100      321       97     348     92                                    286   88       322       95     349     97                                    288   100      324       94     350     100                                   289   82       325       100    351     100                                   291   99       327       100    352     98                                    292   97       328       98     353     100                                   293   97       329       95     354     99                                    296   100      331       78     355     99                                    298   98       333       81     356     99                                    299   98       334       97     357     99                                    300   93       335       100    358     97                                    301   100      336       100    359     100                                   302   80       337       100    360     100                                   303   100      338       100    361     100                                   305   99       339       100    362     98                                    309   100      340       100    363     100                                   310   100      341       100    364     100                                   311   96       342       99     365     100                                   313   93       343       99     366     95                                    314   87       344       99     367     100                                   316   93       345       100    368     100                                   369   100      392       100    415     100                                   370   97       393       99     416     100                                   371   100      394       98     417     99                                    372   96       395       100    418     100                                   373   100      396       100    419     95                                    374   100      397       100    420     100                                   375   96       398       100    471     100                                   376   100      399       99     472     100                                   377   98       400       100    473     99                                    378   100      401       100    474     97                                    379   100      402       98     475     100                                   380   100      403       97     476     100                                   381   100      404       98     477     100                                   382   100      405       100    478     100                                   383   100      406       100    479     100                                   384   100      407       99     480     100                                   385   100      408       100    481     100                                   386   100      409       100    482     99                                    387   99       410       97     483     100                                   388   100      411       97     484     100                                   389   100      412       100    485     96                                    390   99       413       97     486     98                                    391   92       414       87     487     99                                    ______________________________________                                        Compound  Control     Compound   Control                                      No.       value       No.        value                                        tested    (%)         tested     (%)                                          ______________________________________                                        488       90          542        96                                           489       100         543        90                                           490       100         Comparative                                                                   Chemical 1 0                                            491       100                                                                 492       100         Comparative                                                                   Chemical 2 13                                           493       100                                                                 494       100                                                                 495       97                                                                  511       100                                                                 514       100                                                                 515       100                                                                 516       100                                                                 522       98                                                                  525       96                                                                  527       77                                                                  529       91                                                                  530       90                                                                  531       80                                                                  532       88                                                                  534       70                                                                  535       97                                                                  538       98                                                                  541       70                                                                  ______________________________________                                    

                  TABLE 3b                                                        ______________________________________                                        Compound  Control     Compound   Control                                      No.       value       No.        value                                        tested    (%)         tested     (%)                                          ______________________________________                                        544       100         568        100                                          545       100         569        100                                          546       100                                                                                       570        100                                          547       100                                                                                       571        100                                          548       100                                                                 549       100         572        100                                          550       100         573        100                                          551       100                                                                                       574        100                                          552       100                                                                                       575        100                                          553       100                                                                 554       100                                                                 555       100         Comparative                                                                   Chemical 1 0                                            556       100                                                                 557       100         Comparative                                                                   Chemical 2 13                                           558       100                                                                 559       100                                                                 560       100                                                                 561       100                                                                 562       100                                                                 563       100                                                                 565       100                                                                 566       100                                                                 ______________________________________                                    

                  TABLE 3c                                                        ______________________________________                                        Com-                                                                          pound Control  Compound  Control                                                                              Compound                                                                              Control                               No.   value    No.       value  No.     value                                 tested                                                                              (%)      tested    (%)    tested  (%)                                   ______________________________________                                        581   100      602       100    626     100                                   582   100      604       100    627     100                                   583   100      605       100    628     100                                   584   100      606       100    629     100                                   585   100      607       100    630     100                                   586   100      608       100    631     100                                   587   100      609       100    632     100                                   588   100      610       100    633     100                                   589   98.5     611       100    634     100                                   590   100      612       100    635     100                                   591   100      613       100    636     100                                   592   100      614       100    637     100                                   593   100      615       100    638     100                                   594   100      616       100    639     100                                   595   100      617       100    640     100                                   596   100      618       100    641     100                                   597   100      621       100    642     100                                   598   97.8     622       100    643     100                                   599   100      623       100    644     100                                   600   100      624       100    645     100                                   601   100      625       100    646     100                                                                   647     100                                   ______________________________________                                    

                  TABLE 3d                                                        ______________________________________                                                Con-               Con-          Con-                                 Compound                                                                              trol    Compound   trol  Compound                                                                              trol                                 No.     value   No.        value No.     value                                tested  (%)     tested     (%)   tested  (%)                                  ______________________________________                                        648     100     672        81.0  695     100                                  649     91.1    673        100   696     100                                  650     100     674        99.3  697     100                                  651     100     675        100   698     100                                  652     100     676        98.5  699     89.0                                 653     97.6    677        100   700     100                                  654     100     678        100   701     100                                  655     100     679        100   702     100                                  656     88.3    680        100   707     100                                  658     100     681        100   708     100                                  659     100     682        98.5  712     100                                  660     79.3    683        100   713     94.3                                 662     91.2    684        100   714     100                                                                   715     97.7                                 663     100     685        100   716     100                                  664     100     686        100   717     100                                  665     100     687        100   718     100                                  666     100     688        100   719     100                                  667     97.8    689        100   720     100                                  668     100     690        100   721     87.4                                 669     100     691        100   723     82.7                                 670     100     692        100   725     100                                  671     83.9    693        100   726     100                                  ______________________________________                                        Compound  Control    Compound     Control                                     No.       value      No.          value                                       tested    (%)        tested       (%)                                         ______________________________________                                        727       100        757          100                                         728       100        758          100                                         729       100        Comparative                                              730       100        Chemical 1   0                                           731       100        Comparative                                              732       100        Chemical 2   15                                          733       100                                                                 734       100                                                                 735       100                                                                 736       100                                                                 737       88.2                                                                738       100                                                                 739       100                                                                 740       100                                                                 741       100                                                                 742       100                                                                 743       100                                                                 744       100                                                                 745       100                                                                 746       100                                                                 747       100                                                                 755       100                                                                 756       94.9                                                                ______________________________________                                         Note:                                                                         In Tables 3a-3d,                                                              Comparative Chemical 1:                                                       ##STR82##                                                                     (Disclosed in Japanese Patent Application first publication "Kokai" No.       65871/81)                                                                     Comparative Chemical 2:                                                       ##STR83##                                                                     -                                                                             (Disclosed in Japanese Patent Application first publication "Kokai" No.       102504/80)                                                               

TEST 2 (Test on the preventive effects for rice blast, Pyriculariaoryzae)

Unhulled rice seeds (variety: Aichi Asahi) were sown at a rate of 20grains each in white porcelain pots having a diameter of 9 cm. The seedswere allowed to germinate and grow for 3-4 weeks in a greenhouse. Awettable powder containing a test compounds and formulated in accordancewith the procedure of Example 35 was diluted with water to aconcentration of 500 ppm of the active ingredient, and the aqueouspreparation obtained was then sprayed at a rate of 10 ml per pot to therice seedlings at their 4 leaf stage. After dried in the air, theseedlings were inoculated with a spore suspension of rice blast fungi,Pyricularia oryzae and then placed in a moist room at 25° C. On thefifth day after the inoculation, the number of lesions was counted toevaluate the control value. ##EQU2##

Test results obtained are shown in Table 4a-4d. The same comparativechemicals as in Test 1 were also tested in the same manner as above, forthe comparison purpose.

                  TABLE 4a                                                        ______________________________________                                        Com-           Com-                                                           pound Control  pound   Control                                                                              Compound  Control                               No.   value    No.     value  No.       value                                 tested                                                                              (%)      tested  (%)    tested    (%)                                   ______________________________________                                        1     100      82      93     125       83                                    2     94       83      91     129       100                                   6     80       84      83     130       93                                    8     93       89      85     133       84                                    9     78       93      100    135       100                                   13    86       95      92     136       82                                    16    100      97      93     137       94                                    38    90       102     100    145       100                                   52    85       104     85     150       89                                    60    92       106     79     151       93                                    61    89       107     91     153       85                                    65    100      108     83     160       94                                    66    74       109     93     164       93                                    67    83       110     100    165       81                                    68    100      111     90     168       84                                    71    84       112     90     170       100                                   74    90       113     92     173       100                                   76    93       114     88     174       100                                   77    100      117     89     176       100                                   78    100      123     90     177       100                                   79    100      124     89     179       100                                   182   82       260     100    348       92                                    183   82       261     94     349       100                                   186   100      266     73     351       100                                   187   84       272     100    353       90                                    188   80       277     73     354       82                                    194   100      279     81     355       100                                   198   92       288     100    356       100                                   211   100      295     81     357       100                                   213   91       305     90     358       93                                    219   83       310     80     359       100                                   226   100      318     90     360       100                                   227   100      328     90     361       100                                   229   91       335     80     362       100                                   235   94       337     100    364       91                                    244   100      338     88     365       100                                   245   100      339     85     367       93                                    246   100      340     100    370       100                                   247   100      341     84     371       89                                    252   82       342     100    373       84                                    254   81       344     100    374       100                                   255   100      345     100    376       92                                    257   89       346     100    377       88                                    259   89       347     85     379       94                                    380   100      417     100    Comparative                                                                   Chemical 1                                                                              0                                     381   100      418     100                                                    382   100      419     92     Comparative                                                    471     89     Chemical 2                                                                              0                                     383   100      472     100                                                    385   94       473     84                                                     386   93       474     82                                                     387   87       475     92                                                     388   100      476     90                                                     390   100      479     81                                                     392   100      481     90                                                     393   100      489     88                                                     394   100      490     98                                                     395   100      491     94                                                     396   100      493     100                                                    397   100      494     100                                                    398   100      495     100                                                    400   100      511     97                                                     401   86       514     92                                                     408   100      525     100                                                    409   100      526     81                                                     415   90       542     91                                                     416   100                                                                     ______________________________________                                    

                  TABLE 4b                                                        ______________________________________                                               Compound No.                                                                     Control    Compound No. Control                                            tested                                                                           value (%)  tested       value (%)                                   ______________________________________                                               544                                                                              100        565          97.5                                               545                                                                              100        566          99.5                                               546                                                                              100        569          86.9                                               547                                                                              98.9       572          94.5                                               548                                                                              100        573          100                                                549                                                                              100        574          100                                                550                                                                              96.6       575          98.5                                               551                                                                              97.1       576          100                                                552                                                                              97.1       577          98.5                                               553                                                                              98.3       578          100                                                554                                                                              97.1       579          100                                                555                                                                              100                                                                        556                                                                              100        Comparative                                                     557                                                                              100        Chemical 1   0                                                  558                                                                              99.4       Comparative                                                     559                                                                              100        Chemical 2   0                                                  560                                                                              95.7                                                                       561                                                                              100                                                                        562                                                                              97.5                                                                       563                                                                              97.5                                                                       564                                                                              98.5                                                                ______________________________________                                    

                  TABLE 4c                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Control  pound    Control                                                                              pound  Control                                No.    value    No.      value  No.    value                                  tested (%)      tested   (%)    tested (%)                                    ______________________________________                                        581    100      604      98.4   630    100                                    582    100      605      100    631    100                                    583    99.3     606      100    632    85.3                                   584    98.7     607      100    633    100                                    585    99.5     608      100    634    98.0                                   587    100      609      98.0   635    99.3                                   588    100      611      100    636    100                                    589    91.9     612      99.3   637    100                                    590    91.9     613      100    638    100                                    591    98.3     614      91.1   639    100                                    592    100      615      97.4   640    100                                    593    96.8     616      99.0   641    100                                                    617      100                                                  594    99.3     618      100    642    100                                    595    100      621      100    643    98.0                                   596    100      623      98.8   644    99.5                                   597    100      624      100    645    100                                    598    90.5     625      100    646    100                                    599    100      626      98.0   647    100                                    600    100      627      99.3                                                 601    99.3     628      99.3                                                 602    99.0     629      99.3                                                 ______________________________________                                    

                  TABLE 4d                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Control  pound    Control                                                                              pound  Control                                No.    value    No.      value  No.    value                                  tested (%)      tested   (%)    tested (%)                                    ______________________________________                                        648    88.1     677      100    702    100                                    650    100      678      99.4   712    95.8                                   651    97.1     679      98.3   713    100                                    652    91.3     680      92.5   714    90.9                                   653    95.7     681      87.6   716    75.8                                   654    96.3     682      75.8   717    100                                    655    95.7     683      90.0   718    97.4                                   657    71.6     684      75.3   725    92.4                                   658    91.1     685      91.8   726    81.8                                   659    98.6     686      95.9   727    95.0                                   660    99.4     687      88.8   728    81.0                                   661    77.9     688      72.9   730    88.0                                   663    100      689      74.7   731    95.0                                   664    77.5     693      98.5   732    97.6                                   665    100      694      76.8   733    100                                    666    98.3     695      78.1   734    100                                    667    89.6     696      96.9   735    100                                    668    94.8     697      95.9   736    78.3                                   669    96.5     698      96.6   737    68.0                                   670    97.1     700      94.3   738    100                                    673    93.1     701      96.6   739    100                                    740    79.5                                                                   741    95.8                                                                   742    95.2                                                                   743    100                                                                    744    96.4                                                                   745    88.5                                                                   747    100                                                                    755    92.5                                                                   Com-   0                                                                      parative                                                                      Chemical                                                                      Com-   0                                                                      parative                                                                      Chemical                                                                      2                                                                             ______________________________________                                    

TESTS 3 (Test on the preventive effects for cucumber downy mildew,Pseudoperonospora cubensis)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seedseach in PVC-made pots of 9 cm ×9 cm. The seeds were allowed to grow in agreenhouse for 7 days. A wettable powder containing a test compound andformulated in accordance with the procedure of Example 35 was dilutedwith water to concentration of 500 ppm of the active ingredient, and theaqueous preparation obtained was then applied at a rate of 10 ml per potto the cucumber seedlings at their cotyledonous stage. After dried inthe air, the seedlings were sprayed and inoculated with a sporesuspension of cucumber downy mildew fungi, Pseudoperonospora cubensisand then placed in a moist room at 20°-22° C. On the seventh day afterthe inoculation, the extent of lesion was rated in accordance with thefollowing standards and equation to estimate the degree of developmentof disease and the control value.

    ______________________________________                                        Extent of disease:                                                            Healthy:    No lesion was observed.                                           Slight:     Leaf area infected < 1/3 of the whole - leaf area                 Medium:     Leaf area infected: 2/3 to 1/3 of the - whole leaf area           Severe:     Leaf area infected > 2/3 of the whole                                         leaf area                                                         Degree of development of disease (%) =                                        [{(number of healthy leaves × 0) + (number of                           slightly-infected leaves × 1) + (number of                              medium-infected leaves × 2) + (number of                                severely-infected leaves × 3)} ÷ 3N] × 100                    where N denotes the total number of the leave under test.                      ##STR84##                                                                    ______________________________________                                    

Test Results ar shown in Table 5a-5d below. The same comparativechemicals as in Test 1 were also tested in the same procedure as above,for the comparison purpose.

                  TABLE 5a                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Control  pound    Control                                                                              pound  Control                                No.    value    No.      value  No.    value                                  tested (%)      tested   (%)    tested (%)                                    ______________________________________                                        1      83       130      100    195    91                                     2      83       142      92     196    83                                     5      100      143      90     198    86                                     6      92       161      94     210    100                                    7      92       166      100    212    83                                     8      100      168      100    219    82                                     16     100      169      83     226    100                                    17     100      173      100    235    92                                     20     90       174      100    244    100                                    42     92       176      100    245    90                                     52     80       177      90     247    100                                    65     100      178      83     250    100                                    69     100      179      100    254    89                                     73     100      181      100    255    100                                    76     91       182      100    256    92                                     88     100      183      100    258    91                                     91     83       185      92     266    83                                     92     100      186      100    270    83                                     93     100      187      92     328    85                                     96     95       188      88     329    83                                     104    83       194      100    343    85                                                     401      92     Com-   0                                      345    85       402      100    parative                                      346    100      403      90     Chemical 1                                    361    100      404      80     Com-   0                                      362    100      407      92     parative                                      365    92       408      100    Chemical 2                                    374    100      409      100                                                  375    100      416      92                                                   376    100      418      100                                                  377    100      471      100                                                  380    90       478      92                                                   381    100      480      92                                                   382    100      481      92                                                   383    100      482      92                                                   388    100      490      100                                                  390    100      493      100                                                  392    100      495      100                                                  393    90       522      100                                                  394    85       526      100                                                  395    89       527      100                                                  397    100      542      91                                                   398    100                                                                    400    100                                                                    ______________________________________                                    

                  TABLE 5b                                                        ______________________________________                                        Compound No. tested                                                                            Control value (%)                                            ______________________________________                                        547              100                                                          548              83.3                                                         549              100                                                          550              100                                                          551              100                                                          553              100                                                          555              90                                                           557              100                                                          558              100                                                          566              90                                                           573              100                                                          575              100                                                          576              100                                                          577              100                                                          578              100                                                          Comparative Chemical 1                                                                         0                                                            Comparative Chemical 2                                                                         0                                                            ______________________________________                                    

                  TABLE 5c                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Control  pound    Control                                                                              pound  Control                                No.    value    No.      value  No     value                                  tested (%)      tested   (%)    tested (%)                                    ______________________________________                                        581    100      611      100    640    91.7                                   582    91.7     613      100    641    100                                    583    100      615      75.0   642    100                                    584    100      616      100    645    100                                    585    83.8     618      100    646    100                                    587    100      621      100    647    100                                    588    100      623      100                                                  590    91.7     624      100                                                  591    100      625      100                                                  592    100      627      100                                                  595    100      628      100                                                  596    100      630      100                                                  597    100      631      100                                                  600    100      632      100                                                  601    100      633      100                                                  602    100      634      100                                                  604    100      635      100                                                  605    100      636      100                                                  606    100      637      100                                                  607    100      638      91.7                                                 609    91.7     639      100                                                  ______________________________________                                    

                  TABLE 5d                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Control  pound    Control                                                                              pound  Control                                No.    value    No.      value  No.    value                                  tested (%)      tested   (%)    tested (%)                                    ______________________________________                                        648    86.0     685      100    727    100                                    650    100      686      100    728    100                                    651    100      687      100    729    83.3                                   655    80.0     690      100    730    100                                    660    100      693      100    731    100                                    663    100      697      83.3   732    100                                    664    91.7     698      100    733    100                                    665    100      700      100    734    100                                    666    100      701      91.7   735    100                                    667    91.7     702      91.7   736    83.3                                   668    100      707      100    737    83.3                                   669    100      708      100    738    100                                    673    100      710      100    739    100                                    675    100      713      100    742    100                                    676    100      714      100    743    100                                    677    100      716      100    744    83.3                                   678    100      717      100    747    100                                    679    100      718      100    755    100                                    680    100      720      83.3   757    100                                    681    91.7     725      100    758    100                                    684    100      726      100    Com-   0                                                                      parative                                                                      Chemical 1                                                                    Com-   0                                                                      parative                                                                      Chemical 2                                    ______________________________________                                    

TEST 4 (Test on the preventive effects for cucumber gray mold, Botrytiscinerea)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seedseach in PVC-made pots of 9 cm ×9 cm. The seeds were allowed to grow for7 days in a greenhouse. A wettable powder containing a test compound andformulated in accordance with the procedure of Example 35 was dilutedwith water to a concentration of 500 ppm of the active ingredient, andthe aqueous preparation obtained was then sprayed at a rate of 10 ml perpot to the cucumber seedlings at their cotyledonous stage. After driedin the air, the seedlings were sprayed and inoculated with a suspensionof homogenized hypha of cucumber gray fungi, Botrytis cinerea and thenplaced in a moist chamber at 20°-23° C. On the fourth day after theinoculation, the overall extent of development of disease in each potwas rated in accordance with the following standard.

Infection index

0: No lesion was observed. .

1: Infected area of less than 25% of the total leaf area

2: Infected area of 26-50% of the total leaf area

3: Infected area of 51-75% of the total leaf area

4: Infected area of 76% or more of the total leaf area

Results are shown in Table 6a-Table 6c below. The same comparativechemicals as in Test 1 were also tested in the same way as above, forthe comparison purpose.

                  TABLE 6a                                                        ______________________________________                                        Com-            Com-            Com-                                          pound  Infec-   pound    Infec- pound   Infec-                                No.    tion     No.      tion   No      tion                                  tested Index    tested   Index  tested  Index                                 ______________________________________                                         8     0        284      1      387     1                                      15    1        288      1      388     0                                      76    0        305      1      392     0                                      88    0        335      1      393     0                                     135    0        336      0      394     0                                     159    1        337      1      396     0                                     160    1        338      1      397     0                                     174    1        340      1      410     1                                     176    0        351      0      412     1                                     177    1        353      1      471     1                                     178    1        356      0      472     1                                     179    0        357      1      481     1                                     188    1        361      0      490     1                                     193    1        362      0      493     0                                     194    0        365      0      495     1                                     226    1        367      0      525     1                                     244    0        374      0                                                    245    0        381      0      Com-    4                                     246    1        382      1      parative                                                                      Chemical 1                                    247    0        383      0      Com-    4                                     255    1        385      0      parative                                      260    1        386      0      Chemical 2                                    ______________________________________                                    

                  TABLE 6b                                                        ______________________________________                                        Compound No. tested                                                                             Infection Index                                             ______________________________________                                        545               0                                                           547               0                                                           548               0                                                           549               0                                                           551               0                                                           552               0                                                           557               0                                                           558               0                                                           559               1                                                           561               1                                                           565               0                                                           573               0                                                           574               0                                                           575               0                                                           576               0                                                           577               0                                                           578               0                                                           579               0                                                           Comparative Chemical 1                                                                          0                                                           Comparative Chemical 2                                                                          1                                                           ______________________________________                                    

                  TABLE 6c                                                        ______________________________________                                        Compound                                                                              Infec-   Compound  Infec-                                                                              Compound                                                                              Infec-                               No.     tion     No.       tion  No.     tion                                 tested  Index    tested    Index tested  Index                                ______________________________________                                        581     0.0      611       0.0   640     0.0                                  582     0.0      612       0.0   641     1.0                                  583     0.0      613       0.0   642     0.0                                  585     0.0      621       1.0   644     0.0                                  587     0.0      622       0.0   645     0.0                                  588     0.0      623       0.0   646     0.0                                  589     1.0      624       0.5   647     0.0                                  590     0.0      625       0.0                                                591     1.0      626       1.0                                                592     0.0      627       0.0                                                593     0.0      628       0.0                                                595     0.0      629       0.0                                                596     0.0      630       0.0                                                597     0.0      631       0.0                                                599     0.0      632       0.0                                                600     0.0      633       0.0                                                601     0.0      634       0.0                                                                 635       0.0                                                605     0.0                                                                                    636       0.0                                                606     0.0      637       0.0                                                607     0.0      638       1.0                                                608     1.0      639       0.5                                                ______________________________________                                    

TEST 5 (Test on the preventive effects for cucumber powdery mildew,Sphaerotheca fuliginea)

Cucumber seeds (variety: Sagami Hanjiro) were sown at a rate of 12 seedseach in PVC-made pots of 9 cm ×9 cm. The seeds were allowed to germinateand grow for 7 days in a greenhouse. A wettable powder containing a testcompound and formulated in accordance with the procedure of Example 35was diluted with water to a concentration of 500 ppm of the activeingredient, and the aqueous preparation obtained was then sprayed at arate of 10 ml per pot to the cucumber seedlings at their cotyledonousstage. After dried in the air, the seedlings were inoculated with sporesof cucumber powdery mildew fungi, Sphaerotheca fuliginea and then placedin a greenhouse at 25°-30° C. On the tenth day after the inoculation,the overall extent of development of disease in each pot was rated inaccordance with the following standard.

Infection index

0: No lesion was observed.

1: Infected area of less than 25% of the total leaf area.

2: Infected area of 26-50% of the total leaf area

3: Infected area of 51-75% of the total leaf area

4: Infected area of 76% or more of the total leaf area.

Results are shown in Table 7a-Table 7c below. The same comparativechemicals as in Test 1 were also tested in the same way as above, forthe comparison purpose.

                  TABLE 7a                                                        ______________________________________                                        Compound                                                                              Infec-  Compound  Infec-                                                                              Compound Infec-                               No.     tion    No.       tion  No.      tion                                 tested  Index   tested    Index tested   Index                                ______________________________________                                         1      1       245       0     383      1                                     2      1       247       0     385      0                                     5      1       255       0     388      0                                     8      0       288       1     392      0                                     16     1       305       1     393      0                                     93     1       316       1     394      0                                     96     1       335       1     397      0                                    104     1       336       0     400      0                                    130     1       337       0     471      1                                    135     1       338       1     472      0                                    160     1       340       0     490      0                                    173     1       351       0     493      1                                    174     0       356       1     495      1                                    176     1       359       1     511      0                                    179     0       361       0     542      1                                    181     1       362       1                                                   182     1       365       0     Comparative                                                                   Chemical 1                                                                             3                                    183     1       374       1                                                   186     1       376       1     Comparative                                                                   Chemical 2                                                                             4                                    226     0       380       0                                                   241     1       381       0                                                   244     1       382       1                                                   ______________________________________                                    

                  TABLE 7b                                                        ______________________________________                                        Compound No. tested                                                                             Infection Index                                             ______________________________________                                        545               0                                                           546               0                                                           547               0                                                           548               0                                                           549               0                                                           551               0                                                           553               0                                                           557               0                                                           558               0                                                           559               0                                                           561               0                                                           566               0                                                           573               0                                                           574               0                                                           575               0                                                           576               0                                                           577               0                                                           578               0                                                           579               0                                                           Comparative Chemical 1                                                                          3                                                           Comparative Chemical 2                                                                          4                                                           ______________________________________                                    

                  TABLE 7c                                                        ______________________________________                                        Compound                                                                              Infec-   Compound  Infec-                                                                              Compound                                                                              Infec-                               No.     tion     No.       tion  No.     tion                                 tested  Index    tested    Index tested  Index                                ______________________________________                                        581     0.0      611       0.0   640     0.0                                  582     0.0      612       0.0   641     0.0                                  583     0.0      613       0.0   642     0.0                                  584     1.0      616       0.0   645     0.0                                  585     0.0      618       0.0   646     0.0                                  587     0.0      622       1.0   647     0.0                                  588     0.0      623       0.0                                                590     0.0      624       1.0                                                591     0.0      625       0.0                                                592     0.0      627       0.0                                                593     0.0      628       0.0                                                595     0.0      629       0.0                                                596     0.0      630       0.0                                                597     0.0      631       0.0                                                599     0.0      632       0.0                                                600     0.0      633       0.0                                                601     0.0      634       0.0                                                602     0.0      635       0.0                                                604     0.0      636       0.0                                                605     0.0      637       0.0                                                606     0.0      638       0.0                                                607     0.0      639       0.0                                                ______________________________________                                    

TEST 6 (Test on the preventive effects for Alternaria sooty spot ofChinese mustard, Alternaria brassicicola)

Seeds of Chinese mustard were sown at a rate of 12 seeds each inPVC-made pots of 9 cm ×9 xm. The seeds were allowed to row for 7 days ina greenhouse. A wettable powder containing a test compound andformulated in accordance with the procedure of Example 35 was dilutedwith water to concentration of 500 ppm of the active ingredient, and theaqueous preparation obtained was then sprayed at a rate of 10 ml per potto the seedlings of the Chinese mustard at their cotyledon stage. Afterdried in the air, the seedlings were sprayed and inoculated with a sporesuspension of Alternaria sooty spot fungi, Alternaria brassicicola andthen placed in a moist chamber at 30° C. On the third day after theinoculation, the average number of lesions per leaf was determined toestimate the control value in accordance with the following equation.Test Results of rating evaluated in accordance with the followingevaluation standard are given in Table 8a-8c below. ##EQU3##

Again, the same comparative chemicals as those employed in Test 1 werealso tested for the comparison purpose.

                  TABLE 8a                                                        ______________________________________                                        Compound        Compound         Compound                                     No.     Evalu-  No.       Evalu- No.     Evalu-                               tested  ation   tested    ation  tested  ation                                ______________________________________                                         1      A       173       B      288     B                                     2      A       174       A      292     B                                     5      B       176       A      298     B                                     8      A       179       B      299     B                                     9      B       181       B      324     B                                     10     B       182       B      337     A                                     16     A       183       B      341     B                                     18     B       187       A      342     B                                     26     B       194       A      345     B                                     31     B       196       B      351     B                                     35     B       198       A      356     A                                     65     B       219       B      357     A                                     76     A       226       A      358     A                                     91     A       227       A      360     A                                     93     A       244       A      361     A                                    109     B       245       A      362     A                                    110     B       247       A      365     A                                    123     B       249       B      366     B                                    135     B       250       A      373     B                                    159     B       255       A      374     A                                    164     B       259       B      376     A                                    380     B       490       A                                                   381     A       493       B                                                   382     B       525       B                                                   383     A                                                                     385     B       Comparative                                                                   Chemical 1                                                                              D                                                   387     A                                                                                     Comparative                                                   388     A       Chemical 2                                                                              D                                                   390     A                                                                     392     A                                                                     393     A                                                                     394     A                                                                     395     B                                                                     396     A                                                                     397     A                                                                     398     B                                                                     400     A                                                                     408     B                                                                     409     A                                                                     417     B                                                                     472     A                                                                     474     B                                                                     484     B                                                                     ______________________________________                                    

                  TABLE 8b                                                        ______________________________________                                        Compound No.                                                                  tested           Evaluation                                                   ______________________________________                                        545              B                                                            547              B                                                            548              A                                                            549              A                                                            550              B                                                            551              A                                                            553              B                                                            555              B                                                            556              B                                                            557              B                                                            558              A                                                            559              B                                                            560              B                                                            561              A                                                            665              B                                                            566              B                                                            573              B                                                            574              B                                                            575              A                                                            576              A                                                            577              B                                                            578              B                                                            579              B                                                            Comparative                                                                   Chemical 1       D                                                            Comparative                                                                   Chemical 2       D                                                            ______________________________________                                    

                  TABLE 8c                                                        ______________________________________                                        Compound         Compound        Compound                                     No.     Evalu-   No.       Evalu-                                                                              No.     Evalu-                               tested  ation    tested    ation tested  ation                                ______________________________________                                        581     A        609       A     635     A                                    582     A        610       A     636     A                                    583     A        611       A     637     A                                    585     A        612       A     638     A                                    586     C        613       A     639     A                                    587     A        614       B     640     A                                    588     A        615       A     641     A                                    590     A        616       A     642     A                                    591     A        618       A     643     A                                    592     A        621       A     644     A                                    593     C        622       A     645     A                                    595     A        623       A     646     A                                    596     A        624       A     647     A                                    597     A        625       A                                                  599     A        626       A                                                  600     A        627       A                                                  601     A        628       A                                                  602     A        629       A                                                  604     A        630       A                                                  605     A        631       A                                                  606     A        632       A                                                  607     A        633       A                                                  608     A        634       A                                                  ______________________________________                                    

TEST 7 (Test on the preventive effects for rice sheath blight at lowrate application of test compounds)

Each 9 seedlings of rice plants (variety: Kinmaze) were transplanted ina white porcelain pot of 9 cm diameter containing paddy soils. Theplants were allowed to grow to the 7-8 leaf stage in a greenhouse. Awettable powder containing a test compound formulated in accordance withthe procedure of Example 35 was diluted in water to concentrations ofthe active ingredient as specified in the following Table 9. The aqueouspreparation obtained was sprayed onto the rice plants at a rate of 10 mlper pot. After dried in the air, the each plant so treated wasinoculated with an agar disk of the pathogenic fungus of rice sheathblight (Rhizoctonia solani) which has been cultured on a potato dextroseagar medium for 2 days, on the basal part of the sheath. The plantsinoculated were kept in a moist chamber to allow the disease developmentat 28° C. Seven days later, the height of lesion formed on the sheathwas measured.

Then, the control value (%) of the disease provided by the test compoundwas calculated according to the following equation. ##EQU4## The testwas made in three replicates using 3 pots in each plot. The resultsobtained are summarized in Table 9 below.

                  TABLE 9                                                         ______________________________________                                                    Control value (%)                                                             Concentration of the active ingre-                                            dient in the sprayed liquid                                       Compound No.                                                                              preparation                                                       tested      1 ppm        3 ppm   10 ppm                                       ______________________________________                                         93         64.5         79.3    84.3                                         388         89.1         93.9    98.0                                         392         80.0         97.5    99.2                                         135         87.9         91.5    98.6                                         503         86.7         94.7    98.3                                         557         88.9         92.4    96.6                                         558         85.5         94.9    97.5                                         642         96.8         99.4    99.8                                         583         94.2         96.7    97.5                                         693         72.0         81.1    97.2                                         665         60.9         71.7    93.5                                         244         90.0         92.9    98.6                                         472         71.6         85.4    98.1                                         336         66.1         87.6    88.3                                         154         81.2         88.9    97.3                                         632         76.4         97.7    97.7                                         625         81.3         94.6    97.6                                         592         92.5         97.5    98.4                                         659         73.3         97.2    99.1                                         Untreated   0            0       0                                            ______________________________________                                    

In the untreated plot, the average height of the sheath blight lesionsamounted to 10.86 cm.

TEST 8

the procedures of Tests 1 to 6 were respectively repeated using somecompounds of this invention as indicated in Table 10 shown below, aswell as another, comparative compounds A to comparative compound E asindicated in Table 10. The control value (%) for the respective plantdisease was evaluated in the same manner as in Tests 1, 2, 3 and 6, orthe infection index was evaluated in the same manner as in Tests 4 and 5above.

The test results obtained are rated in accordance with the followingevaluation standards:

Class A: Control value of greater than 90%, or Infection index of 0.

Class B: Control value of from 70% and up to 90%, or Infection index of1.

Class C: Control value of greater than 50% and up to 70%, or Infectionindex of 2.

Class D: Control value of less than 50%, or Infection index of 3-4.

The results ar summarised in Table 10 below.

                                      TABLE 10                                    __________________________________________________________________________     ##STR85##                                                                                                   Evaluation of Control value                                                          Cucum-                                                                             Cucum-                                                                             Cucum-                                                                             Alter-                                                  Rice   ber  ber  ber  naria                             Substituents in tested compound                                                                     sheath                                                                            Rice                                                                             downy                                                                              gray powdery                                                                            spoty                             X.sub.l  Y.sub.m                                                                            Z.sub.n                                                                          A R  blight                                                                            blast                                                                            mildew                                                                             mold mildew                                                                             spot                     __________________________________________________________________________    Compound No.                                                                  tested                                                                        93       3,5-(OCH.sub.3).sub.2                                                                  H    H  O CH.sub.3                                                                         A   A  A    D    B    A                        388      3,5-(OCH.sub.3).sub.2                                                                  2-Cl H  O CH.sub.3                                                                         A   A  A    A    A    A                        392      3,5-(OCH.sub.3).sub.2                                                                  4-OCH.sub.3                                                                        H  O CH.sub.3                                                                         A   A  A    A    A    A                        135      2-Cl 5-OCH.sub.3                                                                       H    H  O CH.sub.3                                                                         A   A  C    A    B    B                        503      2-Cl 5-OCH.sub.3                                                                       H    2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        557      2-Cl 3,5-(OCH.sub.3).sub.2                                                             H    2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        558      3,5-(OCH.sub.3).sub.2                                                                  2-F  2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        642      3,5-(OCH.sub.3).sub.2                                                                  2,4-F.sub.2                                                                        2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        583      H        2-Cl 2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        693      3,5-(OCH.sub.3).sub.2                                                                  2-F  2-F                                                                              O Cl A   A  A    A    A    A                        665      3,5-(OCH.sub.3).sub.2                                                                  2-F  2-F                                                                              S CH.sub.3                                                                         A   A  A    A    A    A                        244      H        2,4-F.sub.2                                                                        H  O CH.sub.3                                                                         A   A  A    A    B    A                        472      2-Cl     H    2-F                                                                              O CH.sub.3                                                                         A   A  C    B    A    A                        336      2-Cl     2-Cl H  O CH.sub.3                                                                         A   B  C    A    A    B                        154      2-Cl 3,5-(OCH.sub.3).sub.2                                                             H    H  O CH.sub.3                                                                         A   A  A    A    A    A                        633      3,5-(OCH.sub.3).sub.2                                                                  2-Cl 2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        625      2-Cl 3,5-(OCH.sub.3).sub.2                                                             4-OCH.sub.3                                                                        2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        592      2-Br 3,5-(OCH.sub.3).sub.2                                                             H    2-F                                                                              O CH.sub.3                                                                         A   A  A    A    A    A                        Comparative                                                                   compound A                                                                             H        H    H  O H  B   D  B    D    C    D                        Comparative                                                                            2-Cl     H    H  O H  A   D  D    D    D    B                        compound B                                                                    Comparative                                                                            3-OCH.sub.3                                                                            H    H  O H  A   D  B    D    D    C                        compound C                                                                    Comparative                                                                            H        H    H  O CH.sub.3                                                                         A   D  D    D    D    D                        compound D                                                                    Comparative                                                                            3-CH.sub.3                                                                             H    H  O CH.sub.3                                                                         A   D  D    D    D    C                        compound E                                                                    __________________________________________________________________________     In Table 10 above, when "H" is shown in the columns of "X.sub.l ",            "Y.sub.m " and/or "Z.sub.n ", this again means that the substituent X, Y      and Z are absent, that is say, that the value of l, m and/or n is zero.  

What is claimed is:
 1. A 4(1H)-pyridinone derivative represented by theformula ##STR86## wherein X, Y and Z are the same or different and areindependently a halogen atom, a nitro group, a cyano group, a hydroxygroup, aldehyde group (--CHO), a lower alkyl group, ahalogen-substituted lower alkyl group, a lower cyanoalkyl group, a lowerhydroxyalkyl group, a lower alkoxyalkyl group, a lower alkoxy group, ahalogen-substituted lower alkoxy group, a lower alkoxyalkoxy group, alower alkenyl group, a lower alkenyloxy group, a lower alkynyl group, alower alkynyloxy group, a lower alkanoyl group, a lower alkanoyloxygroup, a phenyl group, a phenoxy group, a carbamoyl group, a loweralkylcarbamoyloxy group, a carboxyl or carboxylate group of the formula--COOR¹ where R¹ is a hydrogen atom or a lower alkyl group, or asubstituted or unsubstituted amino group of the formula ##STR87## whereR² and R³ are the same or different and are each a hydrogen atom, alower alkyl group or a lower alkanoyl group; or X, Y and Z areindependently a group of the formula --(O)_(p) --S--R⁴ is a lower alkylgroup and p is an integer of 0 to 3; or X, Y and Z are independently atrimethylene group or a methylene-dioxo group bonded to and bridgingbetween the adjacent two carbon atoms of the same benzene ring to whichX, Y and Z is linking so that X, Y and Z taken together with said twoadjacent two carbon atoms of the same benzene ring forms a 5-memberedring,l, m and n are independently an integer of 0 to 5, R is a halogenatom, a cyano group, a lower alkyl group, a halogen-substituted loweralkyl group, a lower alkoxy group, a lower alkenyl group, a loweralkynyl group, a phenyl group, a benzyl group, a trimethylsilylethynylgroup, a carboxyl or carboxylate group of the formula --COOR¹ where R¹is as defined above, or a substituted methyl group of the formula --CH₂OR⁵ where R⁵ is a hydrogen atom, a lower alkyl group or a benzoyl group,A is an oxygen atom or a sulfur atom, provided that when R is methyl andA is an oxygen atom, l, m and n do not denote zero simultaneously; andprovided that when R and X are each a methyl group, A is an oxygen atomand l is l, m and n do not denote zero simultaneously, and a salt of thecompound of the formula (I) above.
 2. A compound as claimed in claim 1in which R is a (C₁ -C₆) alkyl group, a halogen atom, a cyano group or acarboxyl or carboxylate group of the formula --COOR¹ where R¹ is ahydrogen atom or a lower alkyl group.
 3. A compound as claimed in claim1, in which R is a (C₁ -C₄) alkyl group, a chlorine atom or a bromineatom.
 4. A compound as claimed in claim 1 in which X, Y and Z are thesame or different and are independently a lower alkyl group, a loweralkoxy group, a halogen-substituted lower alkyl group, a lower alkoxygroup, a halogen-substituted lower alkoxy group, a halogen group, nitrogroup, cyano group, a lower alkenyl group, a lower alkenyloxy group, alower alkynyl group or a lower alkynyloxy group, or X, Y and Z areindependently a trimethylene group or a methylene-dioxo group bonded toand bridging between the adjacent two carbon atoms of the same benzenering to which X, Y or Z is linking so that X, Y or Z taken together withsaid two carbon atoms of the same benzene ring forms a 5-memberedring,l, m and n are independently an integer of 0 to 5, A is an oxygenatom or a sulfur atom.
 5. A compound as claimed in claim 1 in which twoor more groups are present for each of the groups X, Y and Z and theyare the same or different from each other in their nature.
 6. A compoundas claimed in claim 1 in which the sum of l, m and n is equal to 2 orgreater than
 2. 7. A compound as claimed in claim 1 in which X is ahalogen atom or a lower alkoxy group or a combination of halogen atom(s)and lower alkoxy group(s); Y is a halogen atom or a lower alkoxy groupor a combination of halogen atom(s) and lower alkoxy group(s); and Z isa halogen atom or a lower alkoxy group or a combination of halogenatom(s) and lower alkoxy group(s).
 8. A compound as claimed in claim 1in which one, two or three groups for X is or are present therein andpositioned at the 2-position, the 3-position, the 2- and 4-positions,the 3- and 5-positions or the 2-, 3- and 5-positions of the benzene ringto which the group(s) X is or are linking.
 9. A compound as claimed inclaim 1, which is represented by the formula ##STR88## wherein X^(a) isa halogen atom, a nitro group, a cyano group, a hydroxy group, a loweralkyl group, a halogen-substituted lower alkyl group, a lower cyanoalkylgroup, a lower hydroxyalkyl group, a lower alkoxyalkyl group, a loweralkoxy group, a halogen-substituted lower alkoxy group, a loweralkoxyalkoxy group, a lower alkenyl group, a lower alkenyloxy group, alower alkynyl group, a lower alkynyloxy group, a lower alkanoyl group, alower alkanoyloxy group, a phenyl group, a phenoxy group, a carbamoylgroup, a lower alkylcarbamoyloxy group, a carboxyl or carboxylate groupof the formula --COOR¹ where R¹ is a hydrogen atom or a lower alkylgroup, or a substituted or unsubstituted amino group of the formula##STR89## where R² and R³ are the same or different and are each ahydrogen atom, a lower alkyl group or a lower alkanoyl group; or X^(a)is a group of the formula --(O)_(p) --S--R⁴ where R⁴ is a lower alkylgroup and p is an integer of 0 to 3; or X^(a) is a trimethylene group ora methylene-dioxo group bonded to and bridging between the adjacent twocarbon atoms of the same benzene ring to which X^(a) is linking so thatX^(a) taken together with said two adjacent two carbon atoms of thebenzene ring forms a 5-membered ring,Y^(a) is a halogen atom, a nitrogroup, a cyano group, a hydroxy group, a lower alkyl group, ahalogen-substituted lower alkyl group, a lower hydroxyalkyl group, anlower alkoxyalkyl group, a lower alkoxy group, a halogen-substitutedlower alkoxy group, a lower alkoxyalkoxy group, a lower alkenyl group, alower alkneyloxy group, a lower alkynyl group, a lower alkynyloxy group,a lower alkanoyl group, a lower alkanoyloxy group, a carbamoyl group, alower alkylcarbamoyloxy group, a carboxyl or carboxylate group of theformula --COOR¹ where R¹ is a hydrogen atom or a lower alkyl group, orY^(a) is a group of the formula --(O)_(p) --S--R⁴ where R⁴ is a loweralkyl group and p is an integer of 0 to 3; or Y^(a) is a trimethylenegroup or a methylene-dioxo group bonded to and bridging between theadjacent two carbon atoms of the same benzene ring to which Y^(a) islinking so that Y^(a) taken together with said two adjacent carbon atomsof the same benzene ring forms a 5-membered ring, Z^(a) is a halogenatom, a nitro group, a cyano group, a hydroxyl group, aldehyde group(--CHO), a lower alkyl group, a halogen-substituted lower alkyl group, alower hydroxyalkyl group, a lower alkoxyalkyl group, a lower alkoxygroup, a halogen-substituted lower alkoxy group, a lower alkoxyalkoxygroup, a lower alkenyl group, a lower alkenyloxy group, a lower alkynylgroup, a lower alkynyloxy group, a lower alkanoyl group, a loweralkanoyloxy group, a carbamoyl group, a lower alkylcarbamoyloxy group, acarboxyl or carboxylate group of the formula --COOR¹ where R¹ is ahydrogen atom or a lower alkyl group, or Z^(a) is a group of the formula--(O)_(p) --S--R⁴ where R⁴ is a lower alkyl group and p is an integer of0 to 3; or Z^(a) is a trimethylene group or a methylene-dioxo groupbonded to and bridging between the adjacent two carbon atoms of the samebenzene ring to which Z^(a) is linking so that Z^(a) taken together withsaid two adjacent two carbon atoms of the same benzene ring forms a5-membered ring, s is an integer of zero, 1, 2 or 3; t is an integer ofzero, 1 or 2; and r is an integer of zero, 1 or 2, R^(a) is a halogenatom, a cyano group, a lower alkyl group, a halogen-substituted loweralkyl group, a lower alkoxy group, a lower alkenyl group, a loweralkynyl group, a phenyl group, a benzyl group, a trimethylsilyethynylgroup, a carboxyl or carboxylate group of the formula --COOR¹ where R¹is as defined above, or a substituted methyl group of the formula --CH₂OR⁵ where R⁵ is a hydrogen atom, a lower alkyl group or a benzoyl group,provided that when R^(a) is methyl, s, t, and r do not denote zerosimultaneously.
 10. A compound as claimed in claim 1, which isrepresented by the formula ##STR90## wherein X^(b) is a halogen atom ora lower alkoxy group or a combination of halogen atom(s) and loweralkoxy group(s); Y^(b) is a halogen atom, or a lower alkoxy group; andZ^(b) is a halogen atom,s is an integer of zero, 1, 2 or 3; t is aninteger of zero, 1 or 2; and r is an integer of zero, 1 or
 2. R^(b) is alower alkyl group or a halogen atom, provided that when R^(b) is methyl,s, t and r do not denote zero simultaneously.
 11. A compound as claimedin claim 1, which is represented by the formula ##STR91## wherein X, Yand Z are the same or different and are independently a halogen atom, alower alkoxy group, a lower alkenyl group, a lower alkenyloxy group, alower alkynyl group or a lower alkynyloxy group,l, m and n areindependently an integer of 0 to 5, R is a lower alkyl group or ahalogen-substituted lower alkyl group.
 12. A compound as claimed inclaim 1, which is represented by the formula ##STR92## wherein X^(c) isa lower alkyl group; Y^(c) is a halogen atom, a lower alkyl group, or alower alkoxy group; and Z^(c) is a halogen atom,s is an integer of zero,1, 2 or 3; t is an integer of zero, 1 or 2; and r is an integer of zero,1 or 2, R^(c) is a lower alkyl group or a halogen atom, provided thatwhen R^(c) is methyl, s, t and r do not denote zero simultaneously, andprovided that t and r do not denote zero simultaneously.
 13. A compoundas claimed in claim 1 or claim 9, which is selected from a compound ofthe formula: ##STR93##
 14. A compound as claimed in claim 1, selectedfrom the group consisting of ##STR94##
 15. A fungicidal composition foragricultural and horticultural utilities, which comprises a compound ofthe formula (I) as defined in claim 1 or a salt thereof as the activeingredient, in combination with a carrier for the active ingredient.